KR20040083509A - Rewritable optical information recording medium and recording/reproducing method, recording/reproducing device - Google Patents

Abstract

A novel rewritable optical information recording medium having a recording layer made of an organic dye film and capable of reversibly recording and reproducing information by laser light irradiation. A rewritable optical information recording medium having, as a recording film, one or more organic dye films consisting substantially of at least one organic dye compound. Information is recorded and erased by a reversible physical change accompanying laser light irradiation of the organic dye film alone. Specifically, data recording is performed by local physical change by irradiation of recording laser light, and data reproduction is performed by detecting a change in the return light intensity of the reproduction laser light with a power smaller than that of the recording laser light, and recording larger than the power of the reproduction laser light. Data erasing is performed by irradiating continuous light or pulsed light having a laser power smaller than that of the laser light at least once. Physical change is shape change.

Description

RECORDABLE OPTICAL INFORMATION RECORDING MEDIUM AND RECORDING / REPRODUCING METHOD, RECORDING / REPRODUCING DEVICE}

Widely used optical recording media on the market today include recordable organic optical discs (so-called CD-R, DVD-R, etc.), rewritable phase change type optical discs (so-called CD-RW, DVD-RW, etc.), and magneto-optical discs. Etc.

The phase-change optical recording medium of CD-RW or DVD-RW is composed of a material containing a chalcogen element such as Te-Ge-Sb alloy, Ag-In-Sb-Te alloy, etc., but it is toxic to them. In addition, in order to cause phase change and form stable recording marks and erase recording marks, sulfides, oxides, and nitrides such as ZnS, ZnS-SiO ₂ , SiO ₂ , Si ₃ N ₄ , and AlN adjacent to the recording film are used. A dielectric film, and a reflective film such as Ag, Al or Ag alloy, Al alloy or the like are required to improve modulation degree (contrast) of the recording signal and to improve thermal characteristics. To form these thin films, it is necessary to use a vacuum film forming method such as a sputtering method, and since the film structure of the recording medium is complicated and the complexity of the film thickness of each thin film must be precisely controlled, a low cost optical recording medium can be produced. it's difficult.

Magneto-optical recording media generally consist of alloy thin films such as rare earth elements Gd and Tb and transition metals Fe, Ni and Co. These alloy thin films are easily oxidized by moisture or oxygen in the atmosphere, such as SiO ₂ or Si _3. There is a problem in long-term recording stability because a protective film such as N ₄ must prevent contact with outside air. In addition, there is a drawback involving the complexity of requiring the use of a polarizing optical system because, in principle, an external magnetic field is required for recording, and further, the optical Kerr effect is used for the reproduction principle of recording information.

On the other hand, CD-R or DVD-R is an optical recording medium using an organic dye material as a recording film. However, rewriting is not possible as a write once type capable of only one recording.

Rewritable optical recording media made of organic materials have been actively studied because they are excellent in terms of molecular design and synthesis as well as non-toxicity and low cost as optical functional materials.

Until now, as a rewritable optical recording medium using an organic material, a photon mode optical recording medium and a thermal mode (or heat mode) type optical recording medium have been reported.

For example, as a photon mode type, there is a rewritable optical recording medium using photochromism of Fulgide, Spiropyran and Diarylethene. For this rewritable optical recording medium, see Yasushi Yokoyama: 'Fulgides for Memories and Switches', Chem. Rev. 2000, 100, 1717-1739, Garry Berkovic, Valeri Krongauz, Victor Weiss: “Spiropyrans and Spirooxazines for Memories and Switches”, Chem. Rev. 2000, 100, 1741-1753, Masahiro Irie: ‘Diarylethenes for Memories and Switches’, Chem. Rev. 2000, 100, 1685-1716. However, these optical recording media need to use laser light of different wavelengths for recording and reproduction.

In addition, since the photochromic reaction is used for both recording and reproduction, the light resistance to the reproduced light is small, and there is a problem in stability and repeatability. In addition, since they are photon mode, high sensitivity is also high, while there is a lack of thermal stability as well as light resistance.

As a thermal mode rewritable optical recording medium, for example, the optical recording medium described in Japanese Patent Application Laid-open No. Hei 6-60421 is a polyurethane, styrene-butadiene copolymer or the like containing a light absorbing agent such as an inorganic or organic pigment or dye. The shape memory resin is used as a recording layer, and the portion recorded by the laser light is formed by the rapid expansion of the convex ridge due to thermal expansion and solidification. It is made by irradiating laser light for a longer time than the time. Further, Japanese Patent Laid-Open No. Hei 6-1073 discloses an optical recording medium using a recording layer containing a conjugated polymer in which the conformation is changed by thermal energy and a dye having light absorption.

In addition, Japanese Patent Laid-Open No. 9-226249 proposes to rewrite information by reversibly changing the cohesive force between substituents of the central metals in the metal phthalocyanine compound. Only the examples in which a metal phthalocyanine compound is dissolved in a high molecular compound such as polystyrene and polyamide are described.

In addition, Japanese Patent Application Laid-Open No. 9-147414 also uses a photochromic material, a thermochromic material, and an associative dye such as an azaanulene compound such as phthalocyanine as a recording layer. Although a recording medium has been proposed, only embodiments in which a polymer compound such as polystyrene and polymethyl methacrylate are mixed are described.

In these examples, the case where the recording film which disperse | mixed or polymerized all the organic pigment | dye which has light absorption ability to a high molecular compound is described, The mixing ratio (or polymerization ratio) is 20 to 80%. In such a case, when the mixing ratio of the light absorbing dye dispersed in the system is small, the amount of energy absorbed and converted into heat decreases, the recording sensitivity decreases, and the ratio of the dye decreases, making it difficult to obtain a large modulation degree. On the other hand, when the mixing ratio is large, aggregation, segregation, crystallization, and association of the dyes occur nonuniformly, which is a source of signal noise. Moreover, if an appropriate high molecular compound and a polymer are not selected, even if it is disperse | distributing uniformly at the time of film formation, there exists a fault that the change over time of a dispersion state in a preservation state tends to occur easily. In the manufacture of discs, in order to obtain long-term storage stability, it is necessary to select a polymer compound having low hygroscopicity, and thus it is difficult to select a solvent that dissolves the polymer compound and does not attack the substrate. Many have disadvantages of lack of reproducibility.

Further, Japanese Patent No. 3054770 discloses a crystal state in which a recording layer made of an organic thin film crystal having optical anisotropy such as a fatty acid or a fatty acid derivative, a benzoic acid derivative or an n-alkane is accompanied by a change in the orientation direction of a reversible molecule. Although a method of causing a change to detect a difference in polarization characteristics has been described, these organic thin-film crystals have uneven crystallinity, which is likely to increase signal noise level. In addition, as in the case of the magneto-optical disk, there is a problem in that a recording and reproducing apparatus requires a polarizing optical system.

In the optical information recording medium, it is necessary to have a high density recording, moderate recording sensitivity, low noise, high reproducibility, high erasure ratio, and excellent rewriting performance with a large number of iterations, and abundant productivity. The point of structure is practically important. It is also compatible with optical recording media that are widely used now, such as CDs having a laser oscillation wavelength of about 780 nm, DVDs having a wavelength of about 650 nm, and optical discs having a laser oscillation wavelength of around 400 nm, which are considered to be next-generation optical disks. It is desirable to.

The present invention has been made in view of the above-mentioned problems, and an object thereof is to provide a rewritable optical information recording medium which adopts only an organic dye thin film material as a recording film and can satisfy the above requirements. It is an object to provide a recording and reproducing method and a recording and reproducing apparatus.

The present invention relates to a novel rewritable optical information recording medium having a recording layer made of an organic dye film and capable of reversibly recording and erasing information by laser light irradiation. It relates to a playback device.

1 is a schematic sectional view showing a basic configuration example of a CD-R or DVD-R optical information recording medium, FIG. 2 is a schematic sectional view showing another configuration example of an optical information recording medium according to the present invention, and FIG. Fig. 4 is a schematic cross-sectional view showing the basic configuration of an optical information recording medium for recording and reproducing through a light transmitting layer. Fig. 4 is an explanatory diagram of a reflectance calculation method of an optical recording medium in consideration of optical multiple reflection of a multilayer thin film. It is a calculation example of the reflectance in the structure specific example of 3, FIG. 6 is a waveform diagram which shows the signal waveform (oscilloscope image) of the initial recording in Example 1, and FIG. 7 is a signal after erasing in Example 1 Fig. 8 is a waveform diagram showing a waveform (oscilloscope image), and Fig. 8 is a waveform diagram showing a signal waveform (oscilloscope image) of re-gi-roxi in Example 1, and Fig. 9 is a signal waveform of initial recording in Example 2 ( Oscillos Fig. 10 is a waveform diagram showing a signal waveform (oscilloscope image) after erasing in Example 2, and Fig. 11 shows a signal waveform (oscilloscope image) of the regioxy in Example 2; Fig. 12 is a waveform diagram showing a signal waveform (oscilloscope image) after 20 repetitive recording erases in Example 2, and Fig. 13 is a signal waveform (initial oscilloscope image) of initial recording in Example 3; Fig. 14 is a waveform diagram showing a signal waveform (oscilloscope image) after erasing in Example 3, and Fig. 15 is a waveform diagram showing a signal waveform (oscilloscope image) of the regioxy in Example 3; Fig. 16 is a waveform diagram showing an eye pattern (oscilloscope image) of initial recording in Example 3, Fig. 17 is a schematic cross-sectional view of the optical information recording medium of Example 4, and Fig. 18 19 is a waveform diagram showing a signal waveform (oscilloscope image) of initial recording in Example 5, and FIG. 19 is a waveform diagram showing a signal waveform (oscilloscope image) after erasing in Example 5, and FIG. Fig. 21A is a photograph showing waveform traces of deformation on the dye layer side when SEM observation of the peeling interface between the substrate-side dielectric layer and the dye layer after recording is performed, and Fig. 21B is a waveform diagram showing the signal waveform (oscilloscope image) of the regioxy. It is a photograph which shows the deformation | transformation trace of the dye layer side when SEM peeling interface of a board | substrate side dielectric layer and a pigment layer after erasing is carried out, and FIG. 21C is a pigment layer side when SEM peeling interface of a board | substrate side dielectric layer and a pigment layer is observed after rewriting. Fig. 21D is a SEM tube of the surface of the dielectric layer when SEM observed the peeling interface between the substrate-side dielectric layer and the dye layer after recording. It is photograph showing scratch.

[Description of the code]

1: substrate

2: recording layer

3: reflective layer

4: protective film

5, 6, 7: transparent protective layer

8: light transmitting layer

Conventionally, it is considered as an organic dye for write-once type organic optical disks, and some practical use is made of polymethine-based cyanine, azulene-based, squarylium-based dyes, metal complex metal naphthalocyanine-based, metal phthalocyanine-based, porphyrin-based and azo-based. And indoaniline dyes, quinone anthraquinones and naphthoquinones. In the early stage of development, a write-once type organic optical disc having a so-called puncturing mode as a recording principle was put into practical use.

The organic dye optical recording material used in CD-R or DVD-R, which is widely used today, has the optical constant which is changed by thermal decomposition of the organic pigment recording film by local energy by laser irradiation, so that the phase modulation or amplitude of complex reflectance is changed. The change of the return light (reflectance) of the reproduction laser light by modulation is a recording reproduction principle, and it is generally considered that rewriting is impossible.

For the above purpose, the present inventors have not thermally decomposed an organic dye recording film using, as an organic dye, a compound selected from at least one of, for example, an azaanulene compound having a molecular weight of less than 3000 or a metal complex thereof by a predetermined laser light irradiation. In addition, by appropriately selecting the irradiation conditions of the beam light at the time of recording and erasing as these organic pigment | dye bodies without mixing or disperse | distributing to a high molecular compound, the said objective can be achieved by reversibly changing physically, such as deformation | transformation. It was found.

The present invention has been completed based on these findings. That is, the rewritable optical information recording medium of the present invention is a light absorbing organic compound film (organic dye) which consists essentially of at least one or more types of light absorbing organic compounds (including metal complexes) (for example, organic pigment compounds). Film) as one or more recording films, and recording and erasing of information is performed by reversible physical change (for example, shape change such as deformation) accompanying laser light irradiation of the organic dye film alone. . The recording / reproducing method of the present invention also has a rewritable optical information recording medium having, as a recording film, at least one light absorbing organic compound film made of at least one light absorbing organic compound (including a metal complex). Is used for recording and erasing information by reversible physical changes associated with laser light irradiation of the light absorbing organic compound film alone. Further, the recording and reproducing apparatus of the present invention has a rewritable optical information recording medium having, as a recording film, at least one light absorbing organic compound film composed of at least one light absorbing organic compound (including a metal complex). And recording and erasing of information by a reversible physical change accompanying laser light irradiation of the light absorbing organic compound film alone.

Recording to the information recording medium in the present invention is performed by irradiating a laser light corresponding to an absorption wavelength of the light absorbing organic compound (for example, an organic dye) by heating the irradiated portion of the laser light and then quenching. As the laser light, it is preferable to use a small, lightweight semiconductor laser according to the absorption wavelength of the dye to be used. The organic dye thin film of the laser light irradiation part in the recording layer first becomes less viscous with temperature rise, and in some cases it is curved or cavified due to expansion and contraction by melting or sublimation, and consequently deformation accompanied by volume change or mass transfer. This happens. In the case of an optical disk which rotates a medium at high speed, the heating unit is rapidly quenched when the laser spot passes by when the laser light irradiation is stopped after the laser light is irradiated and heated for a short time. At this time, if the cooling rate is equal to or higher than the predetermined critical cooling rate, the deformed portion is solidified in its form and becomes a recording mark.

The information signal reproduction of the recording mark recorded as described above is irradiated with light weaker than the power of light used during recording and erasing described later, and the recording unit and the like as in the case of the conventional CD-R and DVD-R. The difference in the amount of returned light from the unrecorded portion can be detected and used. For example, when deformation due to cavitation occurs in the portion of the recording mark, even if no thermal decomposition reaction of the organic dye occurs, the optical constant of the cavity portion is an extreme value close to n = 1.0, k = 0.0, which is different from the optical constant of the organic dye. Value. In addition, even when accompanied by deformation such as dents or protrusions due to mass transfer, a model in which the film thickness of the organic dye recording film changes locally is established in the recording mark portion, and the optical optical path length (refractive index of the recording layer x film thickness) is established. By locally changing), even if there is no change of the previous optical constant, the phase change of the incident wavefront of the laser light occurs, causing the reflectance change and diffraction phenomenon to modulate the return light amount. Therefore, both the amplitude modulation mode and the phase modulation mode can be selected according to the groove shape of the substrate, so that a sufficient modulation degree (contrast) can be obtained.

Incidentally, the recorded information, i.e., erasing the recording mark, can be performed by heating the recording unit and then cooling it. The recording section or the recording section and the unrecorded section can be heated by laser light irradiation. Therefore, it is possible to erase only by continuously scanning a track in which information is recorded using laser light that is stronger than the laser light at the time of reproduction and weaker than the laser light at the time of recording. In the case of an optical disc for rotating the medium at high speed, the track on which the recording mark is written or a part thereof can be performed by irradiating one or more continuous laser lights. When irradiated light is continuously irradiated, the cooling rate becomes so-called slow cooling below the above-mentioned critical cooling rate, and the portion of the recording film whose temperature around the laser spot rises becomes less viscous, so that material movement is easily performed. It becomes a possible state, and the deformed part is flattened and solidified again at the point of returning to the state before recording by disappearing the trace of the cavitation part of the recording mark.

On the other hand, it is preferable that such physical deformation can occur reversibly only in a recording layer made of an organic dye, from the viewpoint of the recording / erasing / recording repeatability. Therefore, it is preferable that no plastic deformation traces remain at the interface adjacent to the dye layer serving as the recording layer.

However, it is difficult to conclude that the recording principle is due to deformation, and further detailed interpretation of the submicron-sized portion is required later, but the change of the orientation state of the organic pigment molecule, the phase change of the crystal state, and the conformation It is also possible that a physical change other than deformation, such as a change, is simultaneously generated. In any case, it was surprisingly found for the first time that the organic dye film itself can realize a rewritable optical recording medium using a reversible physical change.

(The best form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. On the other hand, in the following description, an optical disc as an optical recording medium has a guide groove on a substrate and a recording layer mainly composed of a reflective film and an organic pigment on the guide groove, and is irradiated with a blue-violet laser light having a wavelength of 350 to 450 nm. Although a medium for recording and reproducing of the present invention is described, the optical recording medium of the present invention is not limited to such a shape or configuration, but has a card, a sheet, or other various shapes, does not have a reflective layer, or has a wavelength of 630. The present invention can also be applied to recording and reproduction by a red laser light of ˜680 nm, a near infrared laser light of a wavelength of 750 to 850 nm, and a short wavelength laser having a wavelength of 350 nm or less.

As an example of applying the present invention to an optical disc, a substrate 1, a recording layer 2, a reflective layer 3, and a protective film 4 as shown in FIG. 1 are laminated in this order, and in the optical disc of FIG. Recording and playback are performed from the side (1). Another layer may exist between the substrate 1 and the recording layer 2, between the recording layer 2 and the reflective layer 3, and between the reflective layer 3 and the protective film 4, and in the example of FIG. ), And the transparent protective films 5 and 6 are formed between the recording layer 2 and the recording layer 2 and the reflective layer 3. In another embodiment, a configuration of an optical disk (hereinafter referred to as DVR-Blue) (hereinafter disclosed in Japanese Patent Application Laid-open No. Hei 10-302310) for recording and reproducing information through a light transmitting layer having a thickness of 10 to 177 mu m, For example, as shown in FIG. 3, the reflective layer 2 and the recording layer 3 are formed in this order on the substrate 1 on which the guide grooves are formed, and the transparent protective layer arbitrarily formed on the recording layer 3. A light transmissive layer 8 is formed with (7) interposed therebetween, and information recording and reproducing are performed on the light transmissive layer 8 side. As a material of the substrate, as shown in FIG. 1, a case where blue violet laser light is irradiated through the substrate 1 is considered. For example, polymer materials such as acrylic resin, polyethylene resin, polycarbonate resin, polyolefin resin, epoxy resin, Transparent materials, such as inorganic materials, such as glass, are used. On the other hand, when the laser irradiation is performed from the light transmissive layer 8 side opposite to the substrate 1 as in the configuration shown in Fig. 3, it is not necessary to satisfy optical requirements as the material of the substrate. You can choose. The material which can be injection-molded, such as an acrylic resin, a polycarbonate resin, a polyolefin resin, is preferable from the mechanical characteristic and productivity calculated | required by a board | substrate. In the surface layer of these substrates, guide grooves and / or prepits of 1 µm or less may be formed spirally or concentrically. These guide grooves and prepits are preferably provided at the time of substrate formation, and can be provided by injection molding using a stamper disc or thermal transfer method using a photopolymer. On the other hand, the same method can be applied to the case where the guide grooves and / or prepits may be formed or provided in the light transmitting layer 8 in FIG. For example, in the case of DVR-Blue, the pitch and depth of the guide groove are preferably selected from the range of 0.2 to 0.80 mu m as the pitch and 20 to 150 nm as the depth.

As a constituent material of the recording layer in the optical recording medium of the present invention, irradiation of laser light having sufficient absorption and having a predetermined energy in the laser wavelength range of interest, for example, the oscillation wavelength range of the semiconductor laser mounted in the recording and reproducing apparatus to be used. It is necessary to locally heat the recording film. The light absorbing organic compound described in the present invention is a compound that absorbs light, and preferably is an organic compound that interacts with light in the wavelength range of 180 to 2000 nm to cause light absorption, luminescence, chemical and physical changes, and the like. It is used as a material to make. As this light absorbing organic compound, especially an organic pigment | dye which acts with the light of an ultraviolet light, visible light, and / or near-infrared wavelength range (preferably ultraviolet light, visible light, and / or near-infrared light in the wavelength range of 350 nm-850 nm). Compounds are preferably used.

Specifically, it is recorded with an oscillation wavelength range of 350-450 nm of a blue violet nitride semiconductor laser, a 600-650 nm red semiconductor laser wavelength used for DVD-R, and a 750-850 nm near-infrared semiconductor laser wavelength used for CD-R. As an example of the organic pigment compound of this invention used for the optical recording medium of this invention, Preferably, it is an azaanulen compound, Furthermore, aza, such as a phthalocyanine, naphthalocyanine, tetraaza porphyrin, a triaza porphyrin, a diaza porphyrin, monoaza porphyrin, etc. It can be found in metal complexes, such as a porphyrin compound and a porphyrin compound, and the mixture which consists of 2 or more types of these.

The azaanulene compound described in the present invention is a compound having at least one or more azaanylene rings in which at least one of the carbon atoms constituting the ring in the cyclic hydrocarbon compound composed of a conjugated double bond is substituted with a nitrogen atom. In this invention, the compound complexed with the metal atom and / or the semimetal atom is also included. In addition, a plurality of azaanulene rings may be bonded via one or two or more linking groups. Examples of preferred compounds include pyrrole rings such as phthalocyanine rings, naphthalocyanine rings, subphthalocyanine rings, monoazaporphyrin rings, diazaporphyrin rings, triazaporphyrin rings, azaporphyrin compounds having tetraazaporphyrin rings, porphyrin compounds, and the like. (Aza) porphyrin compound etc. which have a structure are mentioned. The pyrrole ring which has in these ring structures may have a cyclic ring, respectively, and the substituents of a pyrrole ring-like and / or a cyclic ring may couple through the coupling group. Examples of the condensed compound include compounds in which benzene rings such as dibenzotetraazaporphyrin compound, phthalocyanine compound and naphthalocyanine compound are condensed. Moreover, as another exemplary compound, the compound which has an azaanulene ring which has the structure which the pyrrole rings which have in a ring structure directly bond | bonded, for example, a porphysene ring, a corol ring, is mentioned.

The azaanulene compound used in the present invention is preferably a compound having a monomer structure in which a trivalent metal atom or a semimetal atom having a divalent metal atom or substituent which may have a ligand and / or a ligand is coordinated, and a center. It is a compound which has a dimer structure in a molecule | numerator which two aza anarylene ring couple | bonds with respect to one tri- tetravalent metal atom of a metal atom, and also includes the multimer structure more than a trimer. In particular, the azaanulene compound which may be metal complexed with a molecular weight of less than 3000 is required for the recording layer at the wavelength of the laser light because the absorption wavelength can be arbitrarily selected while the extinction coefficient is maintained by selection of a substituent. It is a very useful organic pigment which can satisfy the optical constant.

Hereinafter, the compound of the recording layer described in the present invention will be described in more detail.

In this invention, the compound illustrated by General formula (1) can be mentioned as a preferable example of an azaanulene compound.

[Wherein, R ¹ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxyl group, a substituted or unsubstituted mercapto group, a substitution or An unsubstituted amino group, X ^{1 to} X ⁸ each independently represent a nitrogen atom or a substituted or unsubstituted methine group, and each of the substituents on R ¹ to R ¹⁶ and the methine group may be bonded together through a linking group, or substituted or It has an oxygen atom, a substituted or unsubstituted sulfur atom, a substituted or unsubstituted nitrogen atom between the carbon-carbon atoms in a hydrocarbon group substituted hydroxyl group, a hydrocarbon group substituted mercapto group, and / or a hydrocarbon group substituted amino group in an unsubstituted hydrocarbon group. Can be. In addition, n represents O or 1, and when n is 0, M represents a divalent metal atom or substituent having a ligand and / or a trivalent or tetravalent metal atom or semimetal atom having a ligand, n When 1, M represents a trivalent metal atom and one hydrogen atom or a tetravalent metal atom]

In the compound represented by the formula (1) of the present invention, specific examples of R ¹ to R ¹⁶ include a hydrogen atom; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Nitro group; Cyano group etc. are mentioned.

As a specific example of a substituted or unsubstituted hydrocarbon group represented by R ¹ to R ¹⁶ , a substituent which may have an oxygen atom, a substituted or unsubstituted sulfur atom, a substituted or unsubstituted nitrogen atom between carbon-carbon atoms in the hydrocarbon group, or Unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, etc. are mentioned.

As a substituted or unsubstituted alkyl group of R ¹ to R ¹⁶ , methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pen Methyl, iso-pentyl, 2-methylbutyl, 1-methylbutyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, cyclopentyl, n-hexyl, 4- Methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2- Dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group, 1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1, 1,2-trimethylbutyl group, 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group , 2,4-dimethylpentyl group, n-octyl group, 2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentyl group, 2,4-dimethylhexyl group, 2,2, 4-trimethylpentyl group, 3,5,5-trimethyl Hexyl group, n-nonyl group, n-decyl group, 4-ethyloctyl group, 4-ethyl-4,5-methylhexyl group, n-undecyl group, n-dodecyl group, 1,3,5,7-tetra Ethyloctyl group, 4-butyloctyl group, 6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group, n-tetradecyl group, n-pentadecyl group, 3,5 -Dimethylheptyl group, 2,6-dimethylheptyl group, 2,4-dimethylheptyl group, 2,2,5,5-tetramethylhexyl group, 1-cyclopentyl-2,2-dimethylpropyl group, 1-cyclo C1-C15 unsubstituted linear, branched, or cyclic alkyl groups such as hexyl-2,2-dimethylpropyl group;

Chloromethyl group, chloroethyl group, bromoethyl group, iodoethyl group, dichloromethyl group, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,2-trichloro Alkyl groups having 1 to 10 carbon atoms substituted with halogen atoms such as ethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, nonafluorobutyl group, and perfluorodecyl group;

Hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-hydroxy-3-methoxypropyl group, 2-hydroxy-3-chloropropyl group, 2-hydroxy Hydroxy-3-ethoxypropyl group, 3-butoxy-2-hydroxypropyl group, 2-hydroxy-3-cyclohexyloxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 4- An alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group such as a hydroxydecaryl group;

Hydroxymethoxymethyl group, hydroxyethoxyethyl group, 2- (2'-hydroxy-1'-methylethoxy) -1-methylethyl group, 2- (3'-fluoro-2'-hydroxypropoxy An alkyl group having 2 to 10 carbon atoms substituted with a hydroxyalkoxy group such as an ethyl group, 2- (3'-chloro-2'-hydroxypropoxy) ethyl group, and hydroxybutoxycyclohexyl group;

Hydroxymethoxymethoxymethyl group, hydroxyethoxyethoxyethyl group, [2 '-(2'-hydroxy-1'-methylethoxy) -1'-methylethoxy] ethoxyethyl group, [2'- (2'-fluoro-1'-hydroxyethoxy) -1'-methylethoxy] ethoxyethyl group, [2 '-(2'-chloro-1'-hydroxyethoxy) -1'-methyl Alkyl groups having 3 to 10 carbon atoms substituted with hydroxyalkoxyalkoxy groups such as ethoxy] ethoxyethyl group;

Cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, 2-cyano-3-methoxypropyl group, 2-cyano-3-chloropropyl group, 2-cya Cyano groups such as no-3-ethoxypropyl group, 3-butoxy-2-cyanopropyl group, 2-cyano-3-cyclohexylpropyl group, 2-cyanopropyl group and 2-cyanobutyl group An alkyl group having 2 to 10 carbon atoms substituted with;

Methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, n-hexyloxyethyl group, (4-methylpentoxy) ethyl group, (1, 3-dimethylbutoxy) ethyl group, (2-ethylhexyloxy) ethyl group, n-octyloxyethyl group, (3,5,5-trimethylhexyloxy) ethyl group, (2-methyl-1-iso-propylpropoxy ) Ethyl group, (3-methyl-1-iso-propylbutyloxy) ethyl group, 2-ethoxy-1-methylethyl group, 3-methoxybutyl group, (3,3,3-trifluoropropoxy) ethyl group, An alkyl group having 2 to 15 carbon atoms substituted with an alkoxy group such as a (3,3,3-trichloropropoxy) ethyl group;

Methoxymethoxymethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyethoxyethyl group, butoxyethoxyethyl group, cyclohexyloxyethoxyethyl group, dekaryloxypropoxyethoxy group, (1,2 -Dimethylpropoxy) ethoxyethyl group, (3-methyl-1-iso-butylbutoxy) ethoxyethyl group, (2-methoxy-1-methylethoxy) ethyl group, (2-butoxy-1-methyl Methoxy) ethyl group, 2- (2'-ethoxy-1'-methylethoxy) -1-methylethyl group, (3,3,3-trifluoropropoxy) ethoxyethyl group, (3,3,3- An alkyl group having 3 to 15 carbon atoms substituted with an alkoxyalkoxy group such as trichloropropoxy) ethoxyethyl group;

Methoxymethoxymethoxymethyl group, methoxyethoxyethoxyethyl group, ethoxyethoxyethoxyethyl group, butoxyethoxyethoxyethyl group, cyclohexyloxyethoxyethoxyethyl group, propoxypropoxypropoxyethyl group, ( An alkyl group of 4 to 15 carbon atoms substituted with an alkoxyalkoxyalkoxy group such as 2,2,2-trifluoroethoxy) ethoxyethoxyethyl group and (2,2,2-trichloroethoxy) ethoxyethoxyethyl group;

Formylmethyl group, 2-oxobutyl group, 3-oxobutyl group, 4-oxobutyl group, 2,6-dioxocyclohexane-1-yl group, 2-oxo-5-t-butylcyclohexane-1-yl group C2-C10 alkyl group substituted by the acyl group, such as these;

Formyloxymethyl group, acetoxyethyl group, propionyloxyethyl group, butanoyloxyethyl group, valeryloxyethyl group, (2-ethylhexanoyloxy) ethyl group, (3,5,5-trimethylhexanoyloxy) ethyl group, (3 An alkyl group having 2 to 15 carbon atoms substituted with an acyloxy group such as a 5,5-trimethylhexanoyloxy) hexyl group, a (3-fluorobutyryloxy) ethyl group, and a (3-chlorobutyryloxy) ethyl group;

Formyloxymethoxymethyl group, acetoxyethoxyethyl group, propionyloxyethoxyethyl group, valeryloxyethoxyethyl group, (2-ethylhexanoyloxy) ethoxyethyl group, (3,5,5-trimethylhexanoyl) Acyloxyalkoxy such as an oxybutoxyethyl group, (3,5,5-trimethylhexanoyloxy) ethoxyethyl group, (2-fluoropropionyloxy) ethoxyethyl group, (2-chloropropionyloxy) ethoxyethyl group An alkyl group having 3 to 15 carbon atoms substituted with a group;

Acetoxymethoxymethoxymethyl group, acetoxyethoxyethoxyethyl group, propionyloxyethoxyethoxyethyl group, valeryloxyethoxyethoxyethyl group, (2-ethylhexanoyloxy) ethoxyethoxyethyl group, (3 Acyloxyalkoxyalkoxy, such as a 5, 5- trimethylhexanoyloxy) ethoxy ethoxy ethyl group, a (2-fluoro propionyloxy) ethoxy ethoxy ethyl group, and (2-chloro propionyloxy) ethoxy ethoxy ethyl group. An alkyl group of 5 to 15 carbon atoms substituted with a group;

Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, butoxycarbonylmethyl group, methoxycarbonylethyl group, ethoxycarbonylethyl group, butoxycarbonylethyl group, (p-ethylcyclohexyloxycarbonyl) cyclohexyl group An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyl group such as a (2,2,3,3-tetrafluoropropoxycarbonyl) methyl group and a (2,2,3,3-tetrachloropropoxycarbonyl) methyl group ;

8 to 15 carbon atoms substituted with aryloxycarbonyl groups such as phenoxycarbonylmethyl group, phenoxycarbonylethyl group, (4-t-butylphenoxycarbonyl) ethyl group, naphthyloxycarbonylmethyl group and biphenyloxycarbonylethyl group An alkyl group;

An alkyl group having 9 to 15 carbon atoms substituted with aralkyloxycarbonyl groups such as benzyloxycarbonylmethyl group, benzyloxycarbonylethyl group, phenethyloxycarbonylmethyl group, and (4-cyclohexyloxybenzyloxycarbonyl) methyl group;

An alkyl group having 4 to 10 carbon atoms substituted with alkenyloxycarbonyl groups such as vinyloxycarbonylmethyl group, vinyloxycarbonylethyl group, allyloxycarbonylmethyl group, cyclopentadienyloxycarbonylmethyl group, and octenoxycarbonylmethyl group;

Methoxycarbonyloxymethyl group, methoxycarbonyloxyethyl group, ethoxycarbonyloxyethyl group, butoxycarbonyloxyethyl group, (2,2,2-trifluoroethoxycarbonyloxy) ethyl group, (2,2 An alkyl group having 3 to 15 carbon atoms substituted with an alkoxycarbonyloxy group such as, 2-trichloroethoxycarbonyloxy) ethyl group;

To methoxymethoxycarbonyloxymethyl group, methoxyethoxycarbonyloxyethyl group, ethoxyethoxycarbonyloxyethyl group, butoxyethoxycarbonyloxyethyl group, (2,2,2-trifluoroethoxy) An alkyl group having 4 to 15 carbon atoms substituted with an alkoxyalkoxycarbonyloxy group such as a oxycarbonyloxyethyl group and a (2,2,2-trichloroethoxy) ethoxycarbonyloxyethyl group;

Dimethylaminomethyl group, diethylaminomethyl group, di-n-butylaminomethyl group, di-n-hexylaminomethyl group, di-n-octylaminomethyl group, di-n-decylaminomethyl group, N-isoamyl-N-methylamino Methyl group, piperidinomethyl group, di (methoxymethyl) aminomethyl group, di (methoxyethyl) aminomethyl group, di (ethoxymethyl) aminomethyl group, di (ethoxyethyl) aminomethyl group, di (propoxyethyl) amino Methyl group, di (butoxyethyl) aminomethyl group, bis (2-cyclohexyloxyethyl) aminomethyl group, dimethylaminoethyl group, diethylaminoethyl group, di-n-butylaminoethyl group, di-n-hexylaminoethyl group, di- n-octylaminoethyl group, di-n-decylaminoethyl group, N-isoamyl-N-methylaminoethyl group, piperidinoethyl group, di (methoxymethyl) aminoethyl group, di (methoxyethyl) aminoethyl group, di ( Ethoxymethyl) aminoethyl group, di (ethoxyethyl) aminoethyl group, di (propoxyethyl) ami Ethyl group, di (butoxyethyl) aminoethyl group, bis (2-cyclohexyloxyethyl) aminoethyl group, dimethylaminopropyl group, diethylaminopropyl group, di-n-butylaminopropyl group, di-n-hexylaminopropyl Group, di-n-octylaminopropyl group, di-n-decylaminopropyl group, N-isoamyl-N-methylaminopropyl group, piperidinopropyl group, di (methoxymethyl) aminopropyl group, di ( Methoxyethyl) aminopropyl group, di (ethoxymethyl) aminopropyl group, di (ethoxyethyl) aminopropyl group, di (propoxyethyl) aminopropyl group, di (butoxyethyl) aminopropyl group, bis ( 2-cyclohexyloxyethyl) aminopropyl group, dimethylaminobutyl group, diethylaminobutyl group, di-n-butylaminobutyl group, di-n-hexylaminobutyl group, di-n-octylaminobutyl group, di -n-decylaminobutyl group, N-isoamyl-N-methylaminobutyl group, piperidinobutyl group, di (methoxymethyl) aminobutyl Group, di (methoxyethyl) aminobutyl group, di (ethoxymethyl) aminobutyl group, di (ethoxyethyl) aminobutyl group, di (propoxyethyl) aminobutyl group, di (butoxyethyl) aminobutyl Alkyl groups having 3 to 20 carbon atoms in which dialkylamino groups such as groups and bis (2-cyclohexyloxyethyl) aminobutyl group are substituted;

3 to 10 carbon atoms substituted with acylamino groups such as acetylaminomethyl group, acetylaminoethyl group, propionylaminoethyl group, butanoylaminoethyl group, cyclohexanecarbonylaminoethyl group, p-methylcyclohexanecarbonylaminoethyl group and succiniminoethyl group An alkyl group;

C2-C10 alkyl group substituted by alkyl sulfone amino groups, such as a methyl sulfone amino methyl group, a methyl sulfone amino ethyl group, an ethyl sulfone amino ethyl group, a propyl sulfone amino ethyl group, and an octyl sulfone amino ethyl group;

Methylsulfonylmethyl group, ethylsulfonylmethyl group, butylsulfonylmethyl group, methylsulfonylethyl group, ethylsulfonylethyl group, butylsulfonylethyl group, 2-ethylhexylsulfonylethyl group, 2,2,3,3-tetrafluoropropyl An alkyl group having 2 to 10 carbon atoms substituted with an alkylsulfonyl group such as a sulfonylmethyl group and a 2,2,3,3-tetrachloropropylsulfonylmethyl group;

Benzenesulfonylmethyl group, benzenesulfonylethyl group, benzenesulfonylpropyl group, benzenesulfonylbutyl group, toluenesulfonylmethyl group, toluenesulfonylethyl group, toluenesulfonylpropyl group, toluenesulfonylbutyl group, xylenesulfonylmethyl group, xylene An alkyl group having 7 to 12 carbon atoms substituted with an arylsulfonyl group such as a sulfonylethyl group, a xylenesulfonylpropyl group, and a xylenesulfonylbutyl group;

Thiadiazolinomethyl group, pyrrolinomethyl group, pyrrolidinomethyl group, pyrazolidinomethyl group, imidazolidinomethyl group, oxazolyl group, triazolinomethyl group, morpholinomethyl group, indolinomethyl group, benzimidazolino C2-C13 alkyl group substituted by heterocyclic groups, such as a methyl group and a carbazolinomethyl group;

Ferrocenylmethyl group, ferrocenylethyl group, ferrocenyl-n-propyl group, ferrocenyl-iso-propyl group, ferrocenyl-n-butyl group, ferrocenyl-iso-butyl group, ferrocenyl-sec-butyl group, ferrocenyl -t-butyl group, ferrocenyl-n-pentyl group, ferrocenyl-iso-pentyl group, ferrocenyl-2-methylbutyl group, ferrocenyl-1-methylbutyl group, ferrocenyl neopentyl group, ferrocenyl-1 , 2-dimethylpropyl group, ferrocenyl-1,1-dimethylpropyl group, ferrocenylcyclopentyl group, ferrocenyl-n-hexyl group, ferrocenyl-4-methylpentyl group, ferrocenyl-3-methylpentyl group, Ferrocenyl-2-methylpentyl group, ferrocenyl-1-methylpentyl group, ferrocenyl-3,3-dimethylbutyl group, ferrocenyl-2,3-dimethylbutyl group, ferrocenyl-1,3-dimethylbutyl group , Ferrocenyl-2,2-dimethylbutyl group, ferrocenyl-1,2-dimethylbutyl group, ferrocenyl-1,1-dimethylbutyl group, ferrocenyl-3-ethylbutyl group, ferrocenyl-2-ethylbutyl Group, ferrocenyl-1-ethylbutyl group, ferrocenyl-1,2,2-trimethylbutyl group, ferrocenyl- 1,1,2-trimethylbutyl group, ferrocenyl-1-ethyl-2-methylpropyl group, ferrocenylcyclohexyl group, ferrocenyl-n-heptyl group, ferrocenyl-2-methylhexyl group, ferrocenyl-3 -Methylhexyl group, ferrocenyl-4-methylhexyl group, ferrocenyl-5-methylhexyl group, ferrocenyl-2,4-dimethylpentyl group, ferrocenyl-n-octyl group, ferrocenyl-2-ethylhexyl group , Ferrocenyl-2,5-dimethylhexyl group, ferrocenyl-2,5,5-trimethylpentyl group, ferrocenyl-2,4-dimethylhexyl group, ferrocenyl-2,2,4-trimethylpentyl group, ferro Cenyl-3,5,5-trimethylhexyl group, ferrocenyl-n-nonyl group, ferrocenyl-n-decyl group,

Cobaltosenylmethyl group, cobaltosenylethyl group,

Nickellocenylmethyl group, nickellocenylethyl group;

Dichloro titanosenyl methyl group, trichloro titanium cyclopentadienyl methyl group, bis (trifluoromethane sulfonato) titanocene methyl group, dichloro zirconocenyl methyl group, dimethyl zirconocenyl methyl group, diethoxy zirconocenyl methyl group, bis (cyclopenta Dienyl) chrome methyl group, bis (cyclopentadienyl) dichloro molybdenum methyl group, bis (cyclopentadienyl) dichloro hafnium methyl group, bis (cyclopentadienyl) dichloro niobium group, bis (cyclopentadienyl) ruthenium methyl group, bis An alkyl group having 11 to 20 carbon atoms substituted with metallocenyl groups such as a (cyclopentadienyl) vanadium methyl group and a bis (cyclopentadienyl) dichlorovanadium methyl group;

Ferrocenylmethoxymethyl group, ferrocenylmethoxyethyl group, ferrocenylmethoxypropyl group, ferrocenylmethoxybutyl group, ferrocenylmethoxypentyl group, ferrocenylmethoxyhexyl group, ferrocenylmethoxyheptyl group, ferrocenylmeth Oxyoctyl group, ferrocenyl methoxynonyl group, ferrocenyl methoxydecyl group, ferrocenyl ethoxymethyl group, ferrocenyl ethoxyethyl group, ferrocenyl ethoxy propyl group, ferrocenyl ethoxy butyl group, ferrocenyl ethoxy pentyl group, Ferrocenylethoxyhexyl group, ferrocenyl ethoxyheptyl group, ferrocenyl ethoxy octyl group, ferrocenyl ethoxy nonyl group, ferrocenyl ethoxydecyl group;

Cobaltosenylmethoxymethyl group and cobaltosenylmethoxyethyl group;

Nickellocenyl methoxymethyl group, nickellocenyl methoxyethyl group;

Dichloro titanosenyl methoxymethyl group, trichloro titanium cyclopentadienyl methoxyethyl group, bis (trifluoromethanesulfonato) titanocene methoxypropyl group, dichloro zirconocenyl methoxy butyl group, dimethyl zirconocenyl methoxy pentyl group , Diethoxy zirconocenyl methoxymethyl group, bis (cyclopentadienyl) chrome methoxyhexyl group, bis (cyclopentadienyl) dichloro hafnium methoxymethyl group, bis (cyclopentadienyl) dichloro nioboxy octyl group, Metallocenylalkyloxy groups such as bis (cyclopentadienyl) ruthenium methoxymethyl group, bis (cyclopentadienyl) vanadium methoxymethyl group, bis (cyclopentadienyl) dichlorovanadiummethoxyethyl group, osmosenylmethoxyethyl group Substituted alkyl group having 12 to 30 carbon atoms;

Ferrocenecarbonyloxymethyl group, ferrocenecarbonyloxyethyl group, ferrocenecarbonyloxypropyl group, ferrocenecarbonyloxybutyl group, ferrocenecarbonyloxypentyl group, ferrocenecarbonyloxyhexyl group, ferrocenecarbonyloxyheptyl group, ferrocenecarbonyl Oxyoctyl group, ferrocenecarbonyloxynonyl group, ferrocenecarbonyloxydecyl group;

Cobaltocenecarbonyloxymethyl group, cobaltocenecarbonyloxyethyl group,

Nickellocenecarbonyloxymethyl group, nickellocenecarbonyloxyethyl group,

Dichloro titanosenylcarbonyloxymethyl group, trichloro titanium cyclopentadienylcarbonyloxyethyl group, bis (trifluoromethanesulfonato) titanocenecarbonyloxymethoxypropyl group, dichlorozirconocenecarbonyloxybutyl group, Dimethyl zirconocene carbonyloxypentyl group, diethoxy zirconocene carbonyloxy methyl group, bis (cyclopentadienyl) chrome carbonyloxyhexyl group, bis (cyclopentadienyl) dichloro hafnium carbonyloxy methyl group, bis ( Cyclopentadienyl) dichloroniobcarbonyloxyoctyl group, bis (cyclopentadienyl) rutheniumcarbonyloxymethyl group, bis (cyclopentadienyl) vanadiumcarbonyloxymethyl group, bis (cyclopentadienyl) dichlorovanadiumcarbonyl C12-C30 substituted by metallocenylcarbonyloxy groups, such as an oxyethyl group and a bis (cyclopentadienyl) osmium carbonyloxyethyl group And the like groups.

As an example of the substituted or unsubstituted aralkyl group of R ¹ to R ¹⁶ , an aralkyl group which may have the same substituent as the above-mentioned alkyl group, preferably a benzyl group, nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, Methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, trifluoromethylbenzyl group, naphthylmethyl group, nitronaphthylmethyl group, cyanonaphthylmethyl group, hydroxynaphthylmethyl group, methylnaphthylmethyl group, trifluoromethylnaph C7-C15 aralkyl groups, such as a methylmethyl group and a fluorene-9-ylethyl group, etc. are mentioned.

As an example of the substituted or unsubstituted aryl group of R ¹ to R ¹⁶ , as the aryl group which may have the same substituent as the above-mentioned alkyl group, preferably a phenyl group, nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenyl group, ethyl Phenyl group, xylyl group, mesityl group, trifluoromethylphenyl group, naphthyl group, nitronaphthyl group, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl group, trifluoromethylnaphthyl group, methoxycarbonylphenyl group, 4 C6-C15 aryl groups, such as a-(5'-methylbenzo groupazol-2'-yl) phenyl group and a dibutylaminocarbonylphenyl group, etc. are mentioned.

Further, the carbon-aryl group, that is, specific examples of the substituted or unsubstituted heteroaryl group of R ¹ ~R ¹⁶ groups for the heteroaryl group between a carbon atom having an oxygen atom, a substituted or unsubstituted sulfur atom, substituted or unsubstituted nitrogen atoms As the heteroaryl group which may have the same substituent as the above-mentioned alkyl group, preferably furanyl group, pyrrolyl group, 3-pyrrolino group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, 1 , 2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, pyridinyl group, pyridazinyl group, Pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indolyl group, thionaphsenyl group, benzimidazolyl group, benzothiazolyl group, benzotriazol-2-yl group, benzotria Zol-1-yl, furinyl, quinolinyl, isoquinolinyl, coumarinyl, cinnaolinyl, quinoxali Group, a di-benzofuranyl group, carbazolyl group, phenanthryl Trojan you group, a phenothiazine thiazinyl group, a furanyl beam group, phthalimido group, a naphthyl already aryl unsubstituted heteroaryl, such as group-group;

Or the following substituents, ie

Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;

Cyano group;

Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, methoxymethyl group, ethoxyethyl group, ethoxyethyl group and trifluoromethyl group; Aralkyl groups such as benzyl and phenethyl; Aryl groups such as phenyl group, tolyl group, naphthyl group, xylyl group, mesyl group, chlorophenyl group and methoxyphenyl group; Methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, 2-ethylhexyloxy group, 3,5,5-trimethyl Alkoxy groups, such as a hexyloxy group, a ferrocene methoxy group, a cobaltoce methoxy group, and a nickellocene methoxy group;

Aralkyloxy groups such as benzyloxy group and phenethyloxy group;

Aryloxy groups such as phenoxy group, tolyloxy group, naphthoxy group, xylyloxy group, mesityloxy group, chlorophenoxy group and methoxyphenoxy group; Alkenyl groups such as vinyl group, allyl group, butenyl group, butadienyl group, pentenyl group, cyclopentadienyl group and octenyl group;

Alkenyloxy groups such as vinyloxy group, allyloxy group, butenyloxy group, butadienyloxy group, pentenyloxy group, cyclopentadienyloxy group and octenyloxy group;

Methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, decylthio group, methoxymethylthio group, ethoxyethylthio group, ethoxy Alkylthio groups such as ethylthio group and trifluoromethylthio group;

Aralkylthio groups such as benzylthio group and phenethylthio group;

Arylthio groups such as phenylthio group, tolylthio group, naphthylthio group, xylylthio group, mesylthio group, chlorophenylthio group and methoxyphenylthio group;

Dialkylamino groups such as dimethylamino group, diethylamino group, dipropylamino group and dibutylamino group;

Acyl groups such as acetyl group, propionyl group, butanoyl group, ferrocenecarbonyl group, cobaltocenecarbonyl group and nickellocenecarbonyl group;

Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, ferrocenemethoxycarbonyl group, 1-methylferrocene-1'-ylmethoxycarbonyl group, cobaltosenylmethoxycarbonyl group, and nickellocenylmethoxycarbonyl group;

Aralkyloxycarbonyl groups such as benzyloxycarbonyl group and phenethyloxycarbonyl group;

Aryloxycarbonyl groups such as phenoxycarbonyl group, tolyloxycarbonyl group, naphthoxycarbonyl group, xylyloxycarbonyl group, mesyloxycarbonyl group, chlorophenoxycarbonyl group and methoxyphenoxycarbonyl group;

Alkenyloxycarbonyl groups such as vinyloxycarbonyl group, allyloxycarbonyl group, butenyloxycarbonyl group, butadienyloxycarbonyl group, cyclopentadienyloxy group, pentenyloxycarbonyl group and octenyloxycarbonyl group;

Methylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentylaminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, nonylaminocarbonyl group, 3,5,5-trimethylhexylaminocarbonyl group, 2-ethyl Monoalkylaminocarbonyl groups having 2 to 10 carbon atoms such as hexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, dipropylaminocarbonyl group, dibutylaminocarbonyl group, dipentylaminocarbonyl group, dihexylaminocarbonyl group, diheptylaminocarbonyl group, Alkylaminocarbonyl groups such as dialkylaminocarbonyl groups having 3 to 20 carbon atoms such as dioctylaminocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, 4-methylpiperazinocarbonyl group, and 4-ethylpiperazinocarbonyl group;

Furanyl, pyrrolyl, 3-pyrrolino, pyrrolidino, 1,3-oxoranyl, pyrazolyl, 2-pyrazolinyl, pyrazolidinyl, imidazolyl, oxazolyl, thia Zolyl group, 1,2,3-oxadiazolyl group, 1,2,3-triazolyl group, 1,2,4-triazolyl group, 1,3,4-thiadiazolyl group, 4H-pyranyl group, Pyridinyl group, piperidinyl group, dioxanyl group, morpholinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, piperazinyl group, triazinyl group, benzofuranyl group, indolyl group, thionaspenyl group, Benzimidazolyl, benzothiazolyl, furinyl, quinolinyl, isoquinolinyl, coumarinyl, cinnolinyl, quinoxalinyl, dibenzofuranyl, carbazolyl, phenantronyl, and phenothia Heterocyclic groups such as a genyl group and a furanyl group;

Metallocenyl groups such as ferrocenyl group, cobaltosenyl group, nickellocenyl group, ruthenosenyl group, osmosenyl group and titanosenyl group; Heteroaryl group substituted by substituents, such as these, is mentioned.

As an example of a substituted or unsubstituted alkenyl group of R ¹ to R ¹⁶ , as the alkenyl group which may have the same substituent as the alkyl group listed above, preferably a vinyl group, propenyl group, 1-butenyl group, iso-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2,2-dicyanovinyl group, 2-cyano C2-C10 alkenyl groups, such as a 2-methyl carboxy vinyl group, 2-cyano-2-methyl sulfone vinyl group, a styryl group, and 4-phenyl-2- butenyl group, are mentioned.

Moreover, as a substituted hydrocarbon group represented by R <^1> -R <^16> , the hydrocarbon group in which the carbon atom couple | bonded with the azaanulene ring directly was substituted by the oxo group is mentioned. As a specific example, Substituted or unsubstituted acyl group; Carboxyl groups; Substituted or unsubstituted hydrocarbonoxycarbonyl groups, such as an alkoxycarbonyl group, an aralkyloxycarbonyl group, an aryloxycarbonyl group, and an alkenyloxycarbonyl group; Aminocarbonyl group; Substituted or unsubstituted hydrocarbon aminocarbonyl groups, such as a mono substituted aminocarbonyl group and a di substituted aminocarbonyl group, etc. are mentioned.

As an example of the substituted or unsubstituted acyl group of R ¹ to R ¹⁶ , as an acyl group which may have the same substituent as the alkyl groups listed above, Preferably, formyl group, methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propyl Carbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonyl group, neopentylcarbonyl group, 2-methylbutylcarbonyl group, benzoyl group, methylbenzoyl group, ethyl Benzoyl group, tolylcarbonyl group, propylbenzoyl group, 4-t-butylbenzoyl group, nitrobenzylcarbonyl group, 3-butoxy-2-naphthoyl group, cinnamoyl group, ferrocenecarbonyl group, 1-methylferrocene-1'-carbonyl group, etc. C1-C15 acyl group is mentioned.

As an example of the substituted or unsubstituted alkoxycarbonyl group of R ¹ to R ¹⁶ , as the alkoxycarbonyl group which may have the same substituent as the above-mentioned alkyl group, preferably a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-prop Foxicarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, iso-pentoxycarbonyl group, neopentoxycarbonyl group, 2-pentoxycarbonyl group, 2 to 11 carbon atoms such as 2-ethylhexyloxycarbonyl group, 3,5,5-trimethylhexyloxycarbonyl group, decaryloxycarbonyl group, cyclohexyloxycarbonyl group, chloroethoxycarbonyl group, hydroxymethoxycarbonyl group and hydroxyethoxycarbonyl group An alkoxycarbonyl group;

Methoxymethoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, propoxyethoxycarbonyl group, butoxyethoxycarbonyl group, pentoxyethoxycarbonyl group, hexyloxyethoxycarbonyl group, butoxybutoxycarbonyl group, hexyl oxy An alkoxycarbonyl group having 3 to 11 carbon atoms in which an alkoxy group such as a sibutoxycarbonyl group, a hydroxymethoxymethoxycarbonyl group, and a hydroxyethoxyethoxycarbonyl group is substituted;

Methoxymethoxymethoxycarbonyl group, methoxyethoxyethoxycarbonyl group, ethoxyethoxyethoxycarbonyl group, propoxyethoxyethoxycarbonyl group, butoxyethoxyethoxycarbonyl group, pentoxyethoxyethoxycarbonyl group, hexyloxy Alkoxycarbonyl groups having 4 to 11 carbon atoms in which alkoxyalkoxy groups such as ethoxyethoxycarbonyl group are substituted;

Ferrocenylmethoxycarbonyl group, ferrocenylethoxycarbonyl group, ferrocenylpropoxycarbonyl group, ferrocenylbutoxycarbonyl group, ferrocenylpentyloxycarbonyl group, ferrocenylhexyloxycarbonyl group, ferrocenylheptyloxycarbonyl group, ferrocenyl octyloxycarbonyl group, ferrocenyl octyloxycarbonyl group Nonyloxycarbonyl group, ferrocenyl decyloxycarbonyl group, cobaltosenyl methoxycarbonyl group, cobaltosenyl ethoxycarbonyl group, nickellocenyl methoxycarbonyl group, nickellocenyl ethoxycarbonyl group, dichloro titanosenyl methoxycarbonyl group, trichloro titanium cyclopenta Dienyl methoxycarbonyl group, bis (trifluoromethanesulfonato) titanocenemethoxycarbonyl group, dichloro zirconocenyl methoxycarbonyl group, dimethyl zirconocenyl methoxycarbonyl group, diethoxy zirconocenyl methoxycarbonyl group, bis (cyclopentadiene Nil) chrome methoxycarbonyl , Bis (cyclopentadienyl) dichlorohafnium methoxycarbonyl group, bis (cyclopentadienyl) dichloroniobmethoxycarbonyl group, bis (cyclopentadienyl) ruthenium methoxycarbonyl group, bis (cyclopentadienyl) vanadium methoxycarbonyl group C1-C20 alkoxycarbonyl group substituted by metallocenyl groups, such as a bis (cyclopentadienyl) dichloro vanadium methoxycarbonyl group and a bis (cyclopentadienyl) osmium methoxycarbonyl group; Etc. can be mentioned.

As an example of the substituted or unsubstituted aralkyloxycarbonyl group of R ¹ to R ¹⁶ , an aralkyloxycarbonyl group which may have the same substituent as the above-mentioned alkyl group, preferably a benzyloxycarbonyl group, nitrobenzyloxycarbonyl group, cyanobenzyloxy Carbonyl group, hydroxybenzyloxycarbonyl group, methylbenzyloxycarbonyl group, trifluoromethylbenzyloxycarbonyl group, naphthylmethoxycarbonyl group, nitronaphthylmethoxycarbonyl group, cyanonaphthylmethoxycarbonyl group, hydroxynaphthylmethoxycarbonyl group, methylnaphthylmethoxy C8-C16 aralkyloxycarbonyl groups, such as a carbonyl group, a trifluoromethyl naphthyl methoxycarbonyl group, and a fluorene-9- ethoxycarbonyl group, etc. are mentioned.

As an example of the substituted or unsubstituted aryloxycarbonyl group of R ¹ to R ¹⁶ , an aryloxycarbonyl group which may have the same substituent as the above-mentioned aryl group, preferably a phenoxycarbonyl group, 2-methylphenoxycarbonyl group, 4-methylphenoxy Cycarbonyl group, 4-t-butylphenoxycarbonyl group, 2-methoxyphenoxycarbonyl group, 4-iso-propylphenoxycarbonyl group, naphthoxycarbonyl group, ferrocenyloxycarbonyl group, cobaltosenyloxycarbonyl group, nickelosenyloxycarbonyl group, C7-C11 aryloxycarbonyl groups, such as a zirconosenyl oxycarbonyl group, an octamethyl ferrocenyl oxycarbonyl group, an octamethyl cobaltocenyl oxycarbonyl group, an octamethyl nickel lozenyl oxycarbonyl group, an octamethyl zirconocenyl oxycarbonyl group, etc. .

As an example of the substituted or unsubstituted alkenyloxycarbonyl group of R ¹ to R ^16, an alkenyloxycarbonyl group which may have the same substituent as the above-mentioned alkyl group, preferably a vinyloxycarbonyl group, propenyloxycarbonyl group, 1-butenyl Oxycarbonyl group, iso-butenyloxycarbonyl group, 1-pentenyloxycarbonyl group, 2-pentenyloxycarbonyl group, cyclopentadienyloxycarbonyl group, 2-methyl-1-butenyloxycarbonyl group, 3-methyl-1-butenyl Oxycarbonyl group, 2-methyl-2-butenyloxycarbonyl group, 2,2-dicyanovinyloxycarbonyl group, 2-cyano-2-methylcarboxyvinyloxycarbonyl group, 2-cyano-2-methylsulfonvinyloxycarbonyl group And alkenyloxycarbonyl groups having 3 to 11 carbon atoms such as styryloxycarbonyl group and 4-phenyl-2-butenyloxycarbonyl group.

As an example of the monosubstituted aminocarbonyl group of R <^1> -R <^{16>, it} is a monosubstituted aminocarbonyl group which may have the same substituent as the above-mentioned alkyl group, Preferably methylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, pentyl Aminocarbonyl group, hexylaminocarbonyl group, heptylaminocarbonyl group, octylaminocarbonyl group, (2-ethylhexyl) aminocarbonyl group, cyclohexylaminocarbonyl group, (3,5,5-trimethylhexyl) aminocarbonyl group, nonylaminocarbonyl group, decylaminocarbonyl group, etc. Monoalkylaminocarbonyl group having 2 to 11 carbon atoms; Benzylaminocarbonyl group, phenethylaminocarbonyl group, (3-phenylpropylaminocarbonyl group, (4-ethylbenzyl) aminocarbonyl group, (4-isopropylbenzyl) aminocarbonyl group, (4-methylbenzyl) aminocarbonyl group, (4-ethylbenzyl C8-C11 mono, such as an aminocarbonyl group, (4-allyl benzyl) aminocarbonyl group, [4- (2-cyanoethyl) benzyl] aminocarbonyl group, and [4- (2-acetoxyethyl) benzyl] aminocarbonyl group Aralkylaminocarbonyl group;

Anilinocarbonyl group, naphthylaminocarbonyl group, toluidinocarbonyl group, xyldinocarbonyl group, ethylanilinocarbonyl group, isopropylanilinocarbonyl group, methoxyanilinocarbonyl group, ethoxyanilinocarbonyl group, chloroanilinocarbonyl group, chloroanilinocarbonyl group Carbonyl group, methoxycarbonylanilinocarbonyl group, ethoxycarbonylanilinocarbonyl group, propoxycarbonylanilinocarbonyl group, 4-methylanilinocarbonyl group, 4-ethylanilinocarbonyl group and the like, and a monoarylaminocarbonyl group having 7 to 11 carbon atoms ;

Monoalkenyl having 3 to 11 carbon atoms such as vinylaminocarbonyl group, allylaminocarbonyl group, butenylaminocarbonyl group, pentenylaminocarbonyl group, hexenylaminocarbonyl group, cyclohexenylaminocarbonyl group, octadienylaminocarbonyl group, and adamantenylaminocarbonyl group Aminocarbonyl group etc. are mentioned.

As an example of the di-substituted aminocarbonyl group of R ¹ to R ^{16, as} the di-substituted aminocarbonyl group which may have the same substituent as the alkyl groups listed above, Preferably, a dimethylaminocarbonyl group, diethylaminocarbonyl group, methylethylaminocarbonyl group, dipropylamino Carbonyl group, dibutylaminocarbonyl group, di-n-hexylaminocarbonyl group, dicyclohexylaminocarbonyl group, dioctylaminocarbonyl group, pyrrolidinocarbonyl group, piperidinocarbonyl group, morpholinocarbonyl group, bis (methoxyethyl) aminocarbonyl group, Bis (ethoxyethyl) aminocarbonyl group, bis (propoxyethyl) aminocarbonyl group, bis (butoxyethyl) aminocarbonyl group, di (acetyloxyethyl) aminocarbonyl group, di (hydroxyethyl) aminocarbonyl group, N-ethyl-N -(2-cyanoethyl) aminocarbonyl group, di (propionyloxyethyl) aminocar Beam group or the like having a carbon number of 3-17 dialkylamino group;

Dialkylalkylcarbonyl groups having 15 to 21 carbon atoms such as dibenzylaminocarbonyl group, diphenethylaminocarbonyl group, bis (4-ethylbenzyl) aminocarbonyl group and bis (4-isopropylbenzyl) aminocarbonyl group;

C13-C15 diarylaminocarbonyl groups, such as a diphenylamino carbonyl group, a ditolylaminocarbonyl group, and N-phenyl-N-tolylaminocarbonyl group;

C5-C13 dialkylaminocarbonyl groups, such as a divinylaminocarbonyl group, a diallylaminocarbonyl group, a dibutenylaminocarbonyl group, a dipentenylaminocarbonyl group, a dihexenylaminocarbonyl group, and an N-vinyl-N-allylaminocarbonyl group;

N-phenyl-N-allylaminocarbonyl group, N- (2-acetyloxyethyl) -N-ethylaminocarbonyl group, N-tolyl-N-methylaminocarbonyl group, N-vinyl-N-methylaminocarbonyl group, N-benzyl- C4-C11 di-substituted aminocarbonyl group which has a substituent selected from substituted or unsubstituted alkyl groups, aralkyl groups, aryl groups, and alkenyl groups, such as N-allylaminocarbonyl group, is mentioned.

As a specific example of the substituted or unsubstituted hydroxyl group represented by R <^1> -R <^16> , A hydroxyl group; Substituted or unsubstituted hydrocarbonoxy group of an alkoxy group, aralkyloxy group, aryloxy group, alkenyloxy group which may have an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom between carbon-carbon atoms is mentioned.

As an example of the substituted or unsubstituted alkoxy group of R <^1> -R <^16> , a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group , n-pentyloxy group, isopentyloxy group, tert-pentyloxy group, sec-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group, 3 -Methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1,1,2 -Trimethylpropoxy group, 1,2,2-trimethylpropoxy group, ethylbutoxy group, 1-ethyl-2-methylpropoxy group, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxy group, methyl Hexyloxy group, dimethylpentyloxy group, ethylpentyloxy group, trimethylbutoxy group, 1-ethyl-1-methylbutoxy group, 1-ethyl-2-methylbutoxy group, 1-ethyl-3-methylbutoxy group, 2- Ethyl-1-methylbutoxy group, 2-ethyl-3-methylbutoxy Period, 1-n-propylbutoxy group, 1-isopropylbutoxy group, 1-isopropyl-2-methylpropoxy group, methylcyclohexyloxy group, n-octyloxy group, 1-methylheptyloxy group, 2- Methylheptyloxy group, 3-methylheptyloxy group, 4-methylheptyloxy group, 5-methylheptyloxy group, 6-methylheptyloxy group, dimethylhexyloxy group, 1-ethylhexyloxy group, 2-ethylhexyl jade Period, 3-ethylhexyloxy group, 4-ethylhexyloxy group, 1-n-propylpentyloxy group, 2-n-propylpentyloxy group, 1-isopropylpentyloxy group, 2-isopropylpentyloxy group, 1-ethyl-1-methylpentyloxy group, 1-ethyl-2-methylpentyloxy group, 1-ethyl-3-methylpentyloxy group, 1-ethyl-4-methylpentyloxy group, 2-ethyl-1- Methylpentyloxy group, 2-ethyl-2-methylpentyloxy group, 2-ethyl-3-methylpentyloxy group, 2-ethyl-4-methylpentyloxy group, 3-ethyl-1-methylpentyloxy group, 3 -Ethyl-2-methylpentyloxy group, 3-ethyl-3-methylpentyloxy group, 3-ethyl-4-methylpentyloxy group, trimethylpentyloxy group, 1-n-butylbutoxy group, 1-isobutylbutoxy group, 1-sec-butylbutoxy group, 1-tert-butylbutoxy group, 2-tert-butylbutoxy group, 1-n-propyl-1-methylbutoxy group , 1-n-propyl-2-methylbutoxy group, 1-n-propyl-3-methylbutoxy group, 1-isopropyl-1-methylbutoxy group, 1-isopropyl-2-methylbutoxy group, 1-iso Propyl-3-methylbutoxy group, 1,1-diethylbutoxy group, 1,2-diethylbutoxy group, 1-ethyl-1,2-dimethylbutoxy group, 1-ethyl-1,3-dimethylbutoxy group, 1-ethyl-2,3-dimethylbutoxy group, 2-ethyl-1,1-dimethylbutoxy group, 2-ethyl-1,2-dimethylbutoxy group, 2-ethyl-1,3-dimethylbutoxy group, 2- Ethyl-2,3-dimethylbutoxy group, 1,1,3,3-tetramethylbutoxy group, 1,2-dimethylcyclohexyloxy group, 1,3-dimethylcyclohexyloxy group, 1,4-dimethylcyclohex Siloxy group, ethylcyclohexyloxy group, n-nonyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, 1-adamantyloxy group , n-pen C1-C15 linear, branched or cyclic unsubstituted alkoxy groups, such as a tadecyloxy group;

Methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, n-propoxyethoxy group, isopropoxyethoxy group, n-butoxyethoxy group, isobutoxyethoxy group, tert-butoxy Ethoxy group, sec-butoxyethoxy group, n-pentyloxyethoxy group, isopentyloxyethoxy group, tert-pentyloxyethoxy group, sec-pentyloxyethoxy group, cyclopentyloxyethoxy group, n-hexyloxyethoxy group, ethylcyclohexyloxyethoxy group, n-nonyloxyethoxy group, (3,5,5-trimethylhexyloxy) ethoxy group, (3,5,5-trimethylhexyloxy ) Butoxy group, n-decyloxyethoxy group, n-undecyloxyethoxy group, n-dodecyloxyethoxy group, 3-methoxy propoxy group, 3-ethoxy propoxy group, 3- (n -Propoxy) propoxy group, 2-isopropoxy propoxy group, 2-methoxybutoxy group, 2-ethoxybutoxy group, 2- (n-propoxy) butoxy group, 4-isopropoxybutoxy group, Alkoxy groups, such as a decarboxyloxyethoxy group and adamantyloxyethoxy group Alkoxy group substituted with a carbon number of 2 to 15;

Methoxy methoxymethoxy group, ethoxymethoxymethoxy group, propoxymethoxymethoxy group, butoxymethoxymethoxy group, methoxyethoxymethoxy group, ethoxyethoxymethoxy group, propoxyoxymethoxy group, part Methoxyethoxymethoxy group, methoxypropoxymethoxy group, ethoxypropoxymethoxy group, propoxypropoxymethoxy group, butoxypropoxymethoxy group, methoxybutoxymethoxy group, ethoxybutoxymethoxy group, propoxy Butoxymethoxy group, butoxybutoxymethoxy group, methoxymethoxyethoxy group, ethoxymethoxyethoxy group, propoxymethoxyethoxy group, butoxymethoxyethoxy group, methoxyethoxyethoxy Time period, ethoxyethoxyethoxy group, propoxyethoxyethoxy group, butoxyethoxyethoxy group, methoxypropoxyethoxy group, ethoxypropoxyethoxy group, propoxypropoxyethoxy group, Butoxy propoxy ethoxy group, methoxy butoxy ethoxy group, ethoxy butoxy ethoxy Groups, propoxybutoxyethoxy groups, butoxybutoxyethoxy groups, methoxymethoxypropoxy groups, ethoxymethoxypropoxy groups, propoxymethoxypropoxy groups, butoxymethoxypropoxy groups, Methoxyethoxy propoxy group, ethoxyethoxy propoxy group, propoxyethoxy propoxy group, butoxyethoxy propoxy group, methoxy propoxy propoxy group, ethoxy propoxy propoxy group, propoxy Propoxy propoxy group, butoxy propoxy propoxy group, methoxy butoxy propoxy group, ethoxy butoxy propoxy group, propoxy butoxy propoxy group, butoxy butoxy propoxy group, methoxy methoxy Butoxy group, ethoxy methoxy butoxy group, propoxy methoxy butoxy group, butoxy methoxy butoxy group, methoxy ethoxy butoxy group, ethoxy ethoxy butoxy group, propoxy methoxy butoxy group, butoxy ethoxy butok Period, methoxy propoxy butoxy group, ethoxy propoxy butoxy group, propoxy To propoxy butoxy group, butoxy propoxy butoxy group, methoxy butoxy butoxy group, ethoxy butoxy butoxy group, propoxy butoxy butoxy group, butoxy butoxy butoxy group, and (4-ethylcyclohexyloxy) Straight chains substituted with alkoxyalkoxy groups such as oxyethoxy groups, (2-ethyl-1-hexyloxy) ethoxypropoxy groups, and [4- (3,5,5-trimethylhexyloxy) butoxy] ethoxy groups Branched or cyclic alkoxy groups having 3 to 15 carbon atoms;

Alkoxycarbonyl groups, such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, n-propoxycarbonylmethoxy group, isopropoxycarbonylmethoxy group, (4'-ethylcyclohexyloxy) carbonylmethoxy group, etc. Substituted alkoxy groups having 3 to 10 carbon atoms; An alkoxy group having 3 to 10 carbon atoms substituted with an acyl group such as an acetylmethoxy group, ethylcarbonylmethoxy group, octylcarbonylmethoxy group, and phenacyloxy group;

An alkoxy group having 3 to 10 carbon atoms substituted with an acyloxy group such as acetyloxymethoxy group, acetyloxyethoxy group, acetyloxyhexyloxy group, butanoyloxycyclohexyloxy group;

Methylaminomethoxy group, 2-methylaminoethoxy group, 2- (2-methylaminoethoxy) ethoxy group, 4-methylaminobutoxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropoxy Period, 2-methylamino-2-methylpropoxy group, 2-ethylaminoethoxy group, 2- (2-ethylaminoethoxy) ethoxy group, 3-ethylaminopropoxy group, 1-ethylaminopropoxy group Substituted with alkylamino groups such as 2-isopropylaminoethoxy group, 2- (n-butylamino) ethoxy group, 3- (n-hexylamino) propoxy group and 4- (cyclohexylamino) butyloxy group An alkoxy group having 2 to 10 carbon atoms;

Alkylaminoalkoxy such as methylaminomethoxymethoxy group, methylaminoethoxyethoxy group, methylaminoethoxypropoxy group, ethylaminoethoxypropoxy group and 4- (2'-isobutylaminopropoxy) butoxy group An alkoxy group having 3 to 10 carbon atoms substituted with a group;

Dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2- (2-dimethylaminoethoxy) ethoxy group, 4-dimethylaminobutoxy group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropoxy Period, 2-dimethylamino-2-methylpropoxy group, 2-diethylaminoethoxy group, 2- (2-diethylaminoethoxy) ethoxy group, 3-diethylaminopropoxy group, 1-diethyl Aminopropoxy group, 2-diisopropylaminoethoxy group, 2- (di-n-butylamino) ethoxy group, 2-piperidylethoxy group, 3- (di-n-hexylamino) propoxy group C3-C15 alkoxy group substituted by dialkylamino groups, such as these;

Dimethylaminomethoxymethoxy group, dimethylaminoethoxyethoxy group, dimethylaminoethoxypropoxy group, diethylaminoethoxypropoxy group, 4- (2'-diisobutylaminopropoxy) butoxy group An alkoxy group having 4 to 15 carbon atoms substituted with an alkylaminoalkoxy group;

Methylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group, 2-n-butylthioethoxy group An alkoxy group having 2 to 15 carbon atoms substituted with an alkylthio group such as a 2-isobutylthioethoxy group and a (3,5,5-trimethylhexylthio) hexyloxy group;

And methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentok Period, iso-pentoxy group, neopentoxy group, 2-methylbutoxy group, 2-ethylhexyloxy group, 3,5,5-trimethylhexyloxy group, decaryloxy group, methoxyethoxy group, ethoxyethoxy group And alkoxy groups having 1 to 10 carbon atoms such as methoxyethoxyethoxy group and ethoxyethoxyethoxy group.

As an example of the substituted or unsubstituted aralkyloxy group of R ¹ to R ^16, an aralkyloxy group which may have the same substituent as the above-mentioned alkyl group, preferably a benzyloxy group, nitrobenzyloxy group, cyanobenzyl jade Period, hydroxybenzyloxy group, methylbenzyloxy group, trifluoromethylbenzyloxy group, naphthyl methoxy group, nitronaphthyl methoxy group, cyanonaphthyl methoxy group, hydroxy naphthyl methoxy group, methyl naphthyl methoxy C7-C15 aralkyloxy groups, such as a time period, a trifluoromethyl naphthyl methoxy group, and a fluorene-9- ylethoxy group, etc. are mentioned.

As an example of the substituted or unsubstituted aryloxy group of R ¹ to R ^{16, as} the aryloxy group which may have the same substituent as the above-mentioned alkyl group, preferably a phenylthio group, 2-methylphenylthio group, or 4-methylphenylthio group , 4-t-butylphenylthio group, 2-methoxyphenylthio group, 4-iso-propylphenylthio group, tolyloxy group, naphthoxy group, ferrocenyloxy group, cobaltosenyloxy group, nickellocenyl jade C6-C18 aryloxy groups, such as a time period, an octamethyl ferrocenyloxy group, an octamethyl cobaltosenyloxy group, and an octamethyl nickel lozenyloxy group, are mentioned.

Moreover, as an example of the substituted or unsubstituted heteroaryloxy group of R <^1> -R <^16> which is an aryloxy group which has an oxygen atom, a substituted or unsubstituted sulfur atom, and a substituted or unsubstituted nitrogen atom between carbon-carbon atoms, the hetero enumerated above Heteroaryloxy group which an aryl group couple | bonds with an oxygen atom is mentioned.

As an example of the substituted or unsubstituted alkenyloxy group of R <^1> -R <^16> , As an alkenyloxy group which may have the same substituent as the above-mentioned alkyl group, Preferably a vinyloxy group, a propenyloxy group, the 1-butenyloxy group, iso-butenyloxy group, 1-pentenyloxy group, 2-pentenyloxy group, 2-methyl-1-butenyloxy group, 3-methyl-1-butenyloxy group, 2-methyl-2-butenyloxy group, cyclopenta Dienyloxy group, 2,2-dicyanovinyloxy group, 2-cyano-2-methylcarboxyvinyloxy group, 2-cyano-2-methylsulfonvinyloxy group, styryloxy group, 4-phenyl-2 -C2-C10 alkenyloxy groups, such as a butenyloxy group and a cinnamil alkoxy group, are mentioned.

Moreover, as a substituted hydrocarbon oxy group represented by R <^1> -R <^16> , the hydrocarbon oxy group in which the carbon atom couple | bonded with the oxygen atom directly couple | bonded with the azaanulene ring was substituted by the oxo group is mentioned. As a specific example, Substituted or unsubstituted acyloxy group; Substituted or unsubstituted hydrocarbon oxycarbonyloxy group, such as an alkoxycarbonyloxy group, an aralkyloxycarbonyloxy group, an aryloxycarbonyloxy group, an alkenyloxycarbonyloxy group; Unsubstituted hydrocarbon aminocarbonyloxy groups, such as a mono substituted aminocarbonyloxy group and a di-substituted aminocarbonyloxy group, etc. are mentioned.

As an example of the substituted or unsubstituted acyloxy group of R <^1> -R <^16> , As an acyloxy group which may have the same substituent as the above-mentioned alkyl group, Preferably it is a formyloxy group, methylcarbonyloxy group, and ethylcarbonyloxy group , n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n -Pentylcarbonyloxy group, iso-pentylcarbonyloxy group, neopentylcarbonyloxy group, 2-methylbutylcarbonyloxy group, benzoyloxy group, methylbenzoyloxy group, ethylbenzoyloxy group, tolylcarbonyloxy group , Propylbenzoyloxy group, 4-t-butylbenzoyloxy group, nitrobenzylcarbonyloxy group, 3-butoxy-2-naphthoyloxy group, cinnamoyloxy group, ferrocenecarbonyloxy group, 1-methylferrocene-1 C1-C15 acyloxy groups, such as a "-carbonyloxy group, are mentioned.

As an example of the substituted or unsubstituted alkoxycarbonyloxy group of R <^1> -R <^16> , As an alkoxycarbonyloxy group which may have the same substituent as the above-mentioned alkyl group, Preferably it is a methoxycarbonyloxy group and an ethoxy carbonbo Nyloxy group, n-propoxycarbonyloxy group, iso-propoxycarbonyloxy group, n-butoxycarbonyloxy group, iso-butoxycarbonyloxy group, sec-butoxycarbonyloxy group, t- Butoxycarbonyloxy group, n-pentoxycarbonyloxy group, iso-pentoxycarbonyloxy group, neopentoxycarbonyloxy group, 2-pentoxycarbonyloxy group, 2-ethylhexyloxycarbonyl jade Period, 3,5,5-trimethylhexyloxycarbonyloxy group, dekaryloxycarbonyloxy group, cyclohexyloxycarbonyloxy group, chloroethoxycarbonyloxy group, hydroxymethoxycarbonyloxy group, hydroxide C2-C11 alkoxycarbonyl jade, such as a oxyethoxycarbonyloxy group Time,;

Methoxymethoxycarbonyloxy group, methoxyethoxycarbonyloxy group, ethoxyethoxycarbonyloxy group, propoxyoxycarbonyloxy group, butoxyethoxycarbonyloxy group, pentoxyethoxycarbon Bonyloxy group, hexyloxyethoxycarbonyloxy group, butoxybutoxycarbonyloxy group, hexyloxybutoxycarbonyloxy group, hydroxymethoxymethoxycarbonyloxy group, hydroxyethoxyethoxycarbon An alkoxycarbonyloxy group having 3 to 11 carbon atoms in which an alkoxy group such as a siloxy group is substituted;

Methoxy methoxy methoxycarbonyloxy group, methoxyethoxyethoxycarbonyloxy group, ethoxyethoxyethoxycarbonyloxy group, propoxyethoxy ethoxycarbonyloxy group, butoxyethoxyethoxy An alkoxycarbonyloxy group having 4 to 11 carbon atoms in which an alkoxyalkoxy group such as a carbonyloxy group, a pentoxyethoxyethoxycarbonyloxy group and a hexyloxyethoxyethoxycarbonyloxy group is substituted;

Ferrocenyl methoxycarbonyloxy group, ferrocenyl ethoxycarbonyloxy group, ferrocenyl propoxycarbonyloxy group, ferrocenyl butoxycarbonyloxy group, ferrocenyl pentyl oxycarbonyloxy group, ferrocenyl hexyloxy car A carbonyloxy group, a ferrocenylheptyloxycarbonyloxy group, a ferrocenyl octyloxy carbonyloxy group, a ferrocenyl nonyloxy carbonyloxy group, a ferrocenyl decyloxy carbonyloxy group,

Cobaltosenyl methoxycarbonyloxy group, cobaltosenylethoxycarbonyloxy group, nickellocenyl methoxycarbonyloxy group, nickellocenyl ethoxycarbonyloxy group, dichloro titanosenyl methoxycarbonyloxy group, Trichloro titanium cyclopentadienyl methoxycarbonyloxy group, bis (trifluoromethanesulfonato) titanocene methoxycarbonyloxy group, dichloro zirconocenyl methoxycarbonyloxy group, dimethyl zirconocenyl methoxy carbono Neyloxy group, diethoxy zirconocenyl methoxycarbonyloxy group, bis (cyclopentadienyl) chrome methoxycarbonyloxy group, bis (cyclopentadienyl) dichloro hafnium methoxycarbonyloxy group, bis (cyclopenta) Dienyl) dichloroniobmethoxycarbonyloxy group, bis (cyclopentadienyl) ruthenium methoxycarbonyloxy group, bis (cyclopentadienyl) vanadium methoxycarbonyloxy group, bis (cyclo C1-C20 alkoxycarbonyloxy group substituted by metallocenyl groups, such as a pentadienyl) dichloro vanadium methoxycarbonyloxy group and a bis (cyclopentadienyl) osmium methoxycarbonyloxy group; Etc. can be mentioned.

As an example of the substituted or unsubstituted aralkyloxycarbonyloxy group of R <^1> -R <^{16>, it} is an aralkyloxycarbonyloxy group which may have the same substituent as the above-mentioned alkyl group, Preferably it is a benzyloxycarbonyloxy group, Nitrobenzyloxycarbonyloxy group, cyanobenzyloxycarbonyloxy group, hydroxybenzyloxycarbonyloxy group, methylbenzyloxycarbonyloxy group, trifluoromethylbenzyloxycarbonyloxy group, naphthyl methoxycarbono Nyloxy group, nitronaphthyl methoxycarbonyloxy group, cyanonaphthyl methoxycarbonyloxy group, hydroxy naphthyl methoxycarbonyloxy group, methylnaphthyl methoxycarbonyloxy group, trifluoromethylnaphthyl methoxycarbon And aralkyloxycarbonyloxy groups having 8 to 16 carbon atoms, such as a silyloxy group and a fluorene-9-ylethoxycarbonyloxy group.

Replacement of R ¹ ~R ¹⁶ or unsubstituted aryloxy carbonyloxy examples of the group, listed above as the aryl group and the aryloxy carbonyloxy group which may have the same substituent group, preferably phenoxycarbonyl group, 2-methyl Phenoxycarbonyloxy group, 4-methylphenoxycarbonyloxy group, 4-t-butylphenoxycarbonyloxy group, 2-methoxyphenoxycarbonyloxy group, 4-iso-propylphenoxycarbonyloxy group, naphthoxycarbon Carbonyloxy group, ferrocenyloxycarbonyloxy group, cobaltocenyloxycarbonyloxy group, nickellocenyloxycarbonyloxy group, zirconosenyloxycarbonyloxy group, octamethyl ferrocenyloxycarbonyloxy group, octa And aryloxycarbonyloxy groups having 7 to 11 carbon atoms, such as a methyl cobaltosenyloxycarbonyloxy group, an octamethylnickelocenyloxycarbonyloxy group, and an octamethyl zirconocenyloxycarbonyloxy group.

As an example of the substituted or unsubstituted alkenyloxycarbonyloxy group of R <^1> -R <^16> , it is an alkenyloxycarbonyloxy group which may have the same substituent as the above-mentioned alkyl group, Preferably a vinyloxycarbonyloxy group, Propenyloxycarbonyloxy group, 1-butenyloxycarbonyloxy group, iso-butenyloxycarbonyloxy group, 1-pentenyloxycarbonyloxy group, 2-pentenyloxycarbonyloxy group, cyclopenta Dienyloxycarbonyloxy group, 2-methyl-1-butenyloxycarbonyloxy group, 3-methyl-1-butenyloxycarbonyloxy group, 2-methyl-2-butenyloxycarbonyloxy group, 2,2-dicyanovinyloxycarbonyloxy group, 2-cyano-2-methylcarboxyvinyloxycarbonyloxy group, 2-cyano-2-methylsulfonvinyloxycarbonyloxy group, styryloxycarbon Alkenyloxycarbonyloxy groups having 3 to 11 carbon atoms such as a carbonyloxy group and a 4-phenyl-2-butenyloxycarbonyloxy group Can be mentioned.

As an example of the monosubstituted aminocarbonyloxy group of R <^1> -R <^{16>, it} is a monosubstituted aminocarbonyloxy group which may have the same substituent as the above-mentioned alkyl group, Preferably it is methylaminocarbonyloxy group and ethylaminocarbono Neyloxy group, propylaminocarbonyloxy group, butylaminocarbonyloxy group, pentylaminocarbonyloxy group, hexylaminocarbonyloxy group, heptylaminocarbonyloxy group, octylaminocarbonyloxy group, (2-ethylhexyl C2-C11, such as an aminocarbonyloxy group, a cyclohexylaminocarbonyloxy group, a (3,5,5-trimethylhexyl) aminocarbonyloxy group, a nonylaminocarbonyloxy group, and a decylaminocarbonyloxy group. Monoalkylaminocarbonyloxy group;

Benzylaminocarbonyloxy group, phenethylaminocarbonyloxy group, (3-phenylpropylaminocarbonyloxy group, (4-ethylbenzyl) aminocarbonyloxy group, (4-isopropylbenzyl) aminocarbonyloxy group , (4-methylbenzyl) aminocarbonyloxy group, (4-ethylbenzyl) aminocarbonyloxy group, (4-allylbenzyl) aminocarbonyloxy group, [4- (2-cyanoethyl) benzyl] amino Monoaralkylaminocarbonyloxy groups having 8 to 11 carbon atoms such as a carbonyloxy group and a [4- (2-acetoxyethyl) benzyl] aminocarbonyloxy group;

Anilinocarbonyloxy group, naphthylaminocarbonyloxy group, toluidinocarbonyloxy group, xyldinocarbonyloxy group, ethylanilinocarbonyloxy group, isopropylanilinocarbonyloxy group, methoxy Anilinocarbonyloxy group, ethoxyanilinocarbonyloxy group, chloroanilinocarbonyloxy group, acetylanilinocarbonyloxy group, methoxycarbonylanilinocarbonyloxy group, ethoxycarbonylanilinocarbon Monoarylaminocarbonyloxy groups having 7 to 11 carbon atoms, such as a carbonyloxy group, propoxycarbonylanilinocarbonyloxy group, 4-methylanilinocarbonyloxy group, and 4-ethylanilinocarbonyl groupoxy group;

Vinylaminocarbonyloxy group, allylaminocarbonyloxy group, butenylaminocarbonyloxy group, pentenylaminocarbonyloxy group, hexenylaminocarbonyloxy group, cyclohexenylaminocarbonyloxy group, octadienyl And C3-C11 monoalkenylaminocarbonyloxy groups, such as an aminocarbonyloxy group and an adamantenylaminocarbonyloxy group, etc. are mentioned.

As an example of the di-substituted aminocarbonyloxy group of R <^1> -R <^{16>, It} is a di-substituted aminocarbonyloxy group which may have the same substituent as the above-mentioned alkyl group, Preferably it is a dimethylaminocarbonyloxy group and diethylaminocarbon Carbonyloxy group, methylethylaminocarbonyloxy group, dipropylaminocarbonyloxy group, dibutylaminocarbonyloxy group, di-n-hexylaminocarbonyloxy group, dicyclohexylaminocarbonyloxy group, dioctyl Aminocarbonyloxy group, pyrrolidinocarbonyloxy group, piperidinocarbonyloxy group, morpholinocarbonyloxy group, bis (methoxyethyl) aminocarbonyloxy group, bis (ethoxyethyl) aminocarbon Neyloxy group, bis (propoxyethyl) aminocarbonyloxy group, bis (butoxyethyl) aminocarbonyloxy group, di (acetyloxyethyl) aminocarbonyloxy group, di (hydroxyethyl) aminocarbon Oxy group, N- ethyl -N- (2- cyanoethyl) amino-carbonyloxy group, a di (propionyloxy ethyl) amino carbonyloxy dialkylamino carbonyloxy group having a carbon number of 3-17 such as a group;

C3-C21 dicarbons, such as a dibenzylaminocarbonyloxy group, a diphenethylaminocarbonyloxy group, a bis (4-ethylbenzyl) amino carbonyloxy group, and a bis (4-isopropyl benzyl) aminocarbonyloxy group Aralkylaminocarbonyloxy group;

C13-C15 diarylaminocarbonyloxy group, such as a diphenylamino carbonyloxy group, a ditolylaminocarbonyloxy group, and N-phenyl-N-tolylaminocarbonyloxy group;

Divinylaminocarbonyloxy group, diallylaminocarbonyloxy group, dibutenylaminocarbonyloxy group, dipentenylaminocarbonyloxy group, dihexenylaminocarbonyloxy group, N-vinyl-N-allylaminocarbon C5-C13 dialkylaminocarbonyloxy groups, such as a neyloxy group;

N-phenyl-N-allylaminocarbonyloxy group, N- (2-acetyloxyethyl) -N-ethylaminocarbonyloxy group, N-tolyl-N-methylaminocarbonyloxy group, N-vinyl-N C4-C11 di-substituted aminocarbons having substituents selected from substituted or unsubstituted alkyl groups, aralkyl groups, aryl groups, alkenyl groups, such as -methylaminocarbonyloxy group and N-benzyl-N-allylaminocarbonyloxy group A carbonyloxy group is mentioned.

As a specific example of the substituted or unsubstituted mercapto group represented by R <^1> -R <^16> , Unsubstituted mercapto group; Substituted or unsubstituted hydrocarbon thio such as an alkylthio group, an aralkylthio group, an arylthio group, an alkenylthio group, etc., which may have an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom between carbon-carbon atoms The group can be mentioned.

As an example of the substituted or unsubstituted alkylthio group of R ¹ to R ^16, an alkylthio group which may have the same substituent as the above-mentioned alkyl group, preferably methylthio group, ethylthio group, n-propylthio group, iso Propylthio group, n-butylthio group, isobutylthio group, tert-butylthio group, sec-butylthio group, n-pentylthio group, isopentylthio group, tert-pentylthio group, sec-pentylthio group, Cyclopentylthio group, n-hexylthio group, methylpentylthio group, dimethylbutylthio group, trimethylpropylthio group, 1-ethylbutylthio group, 2-ethylbutylthio group, 1-ethyl-2-methylpropylthio group , Cyclohexylthio group, methylcyclopentylthio group, n-heptylthio group, methylhexylthio group, dimethylpentylthio group, ethylpentylthio group, trimethylbutylthio group, 1-ethyl-1-methylbutylthio group, 1 -Ethyl-2-methylbutylthio group, 1-ethyl-3-methylbutylthio group, 2-ethyl-1-methylbutylthio group, 2-ethyl-3-methylbutylthio Group, 1-n-propylbutylthio group, 1-isopropylbutylthio group, 1-isopropyl-2-methylpropylthio group, methylcyclohexylthio group, n-octylthio group, 1-methylheptylthio group, 2-methylheptylthio group, 3-methylheptylthio group, 4-methylheptylthio group, 5-methylheptylthio group, 6-methylheptylthio group, 1,1-dimethylhexylthio group, 1,2-dimethylhex Silthio group, 1,3-dimethylhexylthio group, 1,4-dimethylhexylthio group, 1,5-dimethylhexylthio group, 2,2-dimethylhexylthio group, 2,3-dimethylhexylthio group, 2, 4-dimethylhexylthio group, 2,5-dimethylhexylthio group, 3,3-dimethylhexylthio group, 3,4-dimethylhexylthio group, 3,5-dimethylhexylthio group, 4,4-dimethylhexyl tea Ogi, 4,5-dimethylhexylthio group, 1-ethylhexylthio group, 2-ethylhexylthio group, 3-ethylhexylthio group, 4-ethylhexylthio group, 1-n-propylpentylthio group, 2- n-propylpentylthio group, 1-isopropylpentylthio group, 2-isopropylpentylthio group, 1-ethyl-1-methylpentylthio group, 1- Tyl-2-methylpentylthio group, 1-ethyl-3-methylpentylthio group, 1-ethyl-4-methylpentylthio group, 2-ethyl-1-methylpentylthio group, 2-ethyl-2-methylphene Tylthio group, 2-ethyl-3-methylpentylthio group, 2-ethyl-4-methylpentylthio group, 3-ethyl-1-methylpentylthio group, 3-ethyl-2-methylpentylthio group, 3-ethyl 3-methylpentylthio group, 3-ethyl-4-methylpentylthio group, trimethylpentylthio group, 1-n-butylbutylthio group, 1-isobutylbutylthio group, 1-sec-butylbutylthio group, 1-tert-butylbutylthio group, 2-tert-butylbutylthio group, 1-n-propyl-1-methylbutylthio group, ln-propyl-2-methylbutylthio group, 1-n-propyl-3- Methylbutylthio group, 1-isopropyl-1-methylbutylthio group, 1-isopropyl-2-methylbutylthio group, 1-isopropyl-3-methylbutylthio group, diethylbutylthio group, 1-ethyl -1,2-dimethylbutylthio group, 1-ethyl-1,3-dimethylbutylthio group, 1-ethyl-2,3-dimethylbutylthio group, 2-ethyl-1,1-dimethylbutylthio group, 2 -Ethyl-1,2-dimethyl moiety Thiogi, 2-ethyl-1,3-dimethylbutylthio group, 2-ethyl-2,3-dimethylbutylthio group, 1,1,3,3-tetramethylbutylthio group, 1,2-dimethylcyclohex Silthio group, 1,3-dimethylcyclohexylthio group, 1,4-dimethylcyclohexylthio group, ethylcyclohexylthio group, n-nonylthio group, 3,5,5-trimethylhexylthio group, n-decylti Linear, branched or cyclic unsubstituted alkylthio groups having 1 to 15 carbon atoms, such as a group, an n-undecylthio group, an n-dodecylthio group, a 1-adamantylthio group, and an n-pentadecylthio group; Methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group, n-propoxyethylthio group, isopropoxyethylthio group, n-butoxyethylthio group, isobutoxyethylthio group, tert-part Methoxyethylthio group, sec-butoxyethylthio group, n-pentyloxyethylthio group, isopentyloxyethylthio group, tert-pentyloxyethylthio group, sec-pentyloxyethylthio group, cyclopentyloxyethylthio group , n-hexyloxyethylthio group, ethylcyclohexyloxyethylthio group, n-nonyloxyethylthio group, (3,5,5-trimethylhexyloxy) ethylthio group, (3,5,5-trimethylhex Siloxy) butylthio group, n-decyloxyethylthio group, n-undecyloxyethylthio group, n-dodecyloxyethylthio group, 3-methoxypropylthio group, 3-ethoxypropylthio group, 3 -(n-propoxy) propylthio group, 2-isopropoxypropylthio group, 2-methoxybutylthio group, 2-ethoxybutylthio group, 2- (n-propoxy) butylthio group, 4- Isopropoxybutyl tea Group, a big reel oxyethyl thio, adamantyloxy ethyl alkylthio group of 2 to 15 carbon atoms substituted with an alkoxy group such as a get tea;

Methoxymethoxymethylthio group, ethoxymethoxymethylthio group, propoxymethoxymethylthio group, butoxymethoxymethylthio group, methoxyethoxymethylthio group, ethoxyethoxymethylthio group, propoxy Ethoxymethylthio group, butoxyethoxymethylthio group, methoxypropoxymethylthio group, ethoxypropoxymethylthio group, propoxypropoxymethylthio group, butoxypropoxymethylthio group, methoxybutoxy Methylthio group, ethoxybutoxymethylthio group, propoxybutoxymethylthio group, butoxybutoxymethylthio group, methoxymethoxyethylthio group, ethoxymethoxyethylthio group, propoxymethoxyethyl thi Oxy, butoxymethoxyethylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, propoxyethoxyethylthio group, butoxyethoxyethylthio group, methoxypropoxyethylthio group, Ethoxypropoxyethylthio group, propoxypropoxyethylthio group, butoxyprop Foxy ethylthio group, methoxybutoxyethylthio group, ethoxybutoxyethylthio group, propoxybutoxyethylthio group, butoxybutoxyethylthio group, methoxymethoxypropylthio group, ethoxymethoxypropyl Thio, propoxymethoxypropylthio group, butoxymethoxypropylthio group, methoxyethoxypropylthio group, ethoxyethoxypropylthio group, propoxyethoxypropylthio group, butoxyethoxypropylthio group , Methoxypropoxypropylthio group, ethoxypropoxypropylthio group, propoxypropoxypropylthio group, butoxypropoxypropylthio group, methoxybutoxypropylthio group, ethoxybutoxypropylthio group, pro Foxoxybutoxypropylthio group, butoxybutoxypropylthio group, methoxymethoxybutylthio group, ethoxymethoxybutylthio group, propoxymethoxybutylthio group, butoxymethoxybutylthio group, methoxy Oxybutylthio group, ethoxyethoxy part Thio group, propoxyoxybutylthio group, butoxyethoxybutoxy group, methoxypropoxybutylthio group, ethoxypropoxybutylthio group, propoxypropoxybutylthio group, butoxypropoxybutylthio group, Methoxybutoxybutylthio group, ethoxybutoxybutylthio group, propoxybutoxybutylthio group, butoxybutoxybutylthio group, (4-ethylcyclohexyloxy) ethoxyethylthio group, (2- Linear, branched or cyclic carbon atoms substituted with an alkoxyalkoxy group such as ethyl-1-hexyloxy) ethoxypropylthio group and [4- (3,5,5-trimethylhexyloxy) butoxy] ethylthio group 3 to 15 alkylthio groups;

Methoxycarbonylmethylthio group, ethoxycarbonylmethylthio group, n-propoxycarbonylmethylthio group, isopropoxycarbonylmethylthio group, (4'-ethylcyclohexyloxy) carbonylmethylthio group C3-C10 alkylthio group substituted by alkoxycarbonyl groups, such as these;

An alkylthio group having 3 to 10 carbon atoms substituted with an acyl group such as acetylmethylthio group, ethylcarbonylmethylthio group, octylcarbonylmethylthio group, and phenacylthio group;

C3-C10 alkylthio group substituted by the acylthio group, such as the acetyloxymethylthio group, the acetyloxyethylthio group, the acetyloxyhexylthio group, butanoyloxycyclohexylthio group;

Methylaminomethylthio group, 2-methylaminoethylthio group, 2- (2-methylaminoethoxy) ethylthio group, 4-methylaminobutylthio group, 1-methylaminopropan-2-ylthio group, 3-methyl Aminopropylthio group, 2-methylamino-2-methylpropylthio group, 2-ethylaminoethylthio group, 2- (2-ethylaminoethoxy) ethylthio group, 3-ethylaminopropylthio group, 1-ethyl Such as aminopropylthio group, 2-isopropylaminoethylthio group, 2- (n-butylamino) ethylthio group, 3- (n-hexylamino) propylthio group, and 4- (cyclohexylamino) butylthio group An alkylthio group having 2 to 10 carbon atoms substituted with an alkylamino group;

Alkyl, such as methyl amino methoxy methylthio group, methyl amino ethoxy ethylthio group, methyl amino ethoxy propyl thio group, ethyl amino ethoxy propyl thio group, and 4- (2'-isobutylamino propoxy) butylthio group An alkylthio group having 3 to 10 carbon atoms substituted with an aminoalkylthio group;

Dimethylaminomethylthio group, 2-dimethylaminoethylthio group, 2- (2-dimethylaminoethoxy) ethylthio group, 4-dimethylaminobutylthio group, 1-dimethylaminopropan-2-ylthio group, 3-dimethyl Aminopropylthio group, 2-dimethylamino-2-methylpropylthio group, 2-diethylaminoethylthio group, 2- (2-diethylaminoethoxy) ethylthio group, 3-diethylaminopropylthio group, 1-diethylaminopropylthio group, 2-diisopropylaminoethylthio group, 2- (di-n-butylamino) ethylthio group, 2-piperidylethylthio group, 3- (di-n-hexyl C3-C15 alkylthio group substituted by dialkylamino groups, such as amino) propylthio group;

Dimethylaminomethoxymethylthio group, dimethylaminoethoxyethylthio group, dimethylaminoethoxypropylthio group, diethylaminoethoxypropylthio group, 4- (2'-diisobutylaminopropoxy) butylthio group, etc. An alkylthio group having 4 to 15 carbon atoms substituted with a dialkylaminoalkylthio group of;

Methylthiomethylthio group, 2-methylthioethylthio group, 2-ethylthioethylthio group, 2-n-propylthioethylthio group, 2-isopropylthioethylthio group, 2-n-butylthioethylthio group An alkylthio group having 2 to 15 carbon atoms substituted with an alkylthio group such as a 2-isobutylthioethylthio group and a (3,5,5-trimethylhexylthio) hexylthio group;

Etc., methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butyl Thio, n-pentylthio group, iso-pentylthio group, neopentylthio group, 2-methylbutylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexyl tea Ogi, 3,5,5-trimethylhexylthio group, decarylthio group, methoxyethylthio group, ethoxyethylthio group, methoxyethoxyethylthio group, ethoxyethoxyethylthio group, n-decylthio group C1-C10 alkylthio groups, such as these, are mentioned.

As an example of the substituted or unsubstituted aralkylthio group of R ¹ to R ^16, an aralkylthio group which may have the same substituent as the above-mentioned alkyl group, preferably a benzylthio group, nitrobenzylthio group, cyanobenzylti Ogi, hydroxybenzylthio group, methylbenzylthio group, trifluoromethylbenzylthio group, naphthylmethylthio group, nitronaphthylmethylthio group, cyanonaphthylmethylthio group, hydroxynaphthylmethylthio group, And aralkylthio groups having 7 to 15 carbon atoms such as methylnaphthylmethylthio group, trifluoromethylnaphthylmethylthio group, and fluorene-9-ylethylthio group.

As an example of the substituted or unsubstituted arylthio group of R ¹ to R ^16, an arylthio group which may have the same substituent as the above-mentioned alkyl group, preferably a phenylthio group, 2-methylphenylthio group, or 4-methylphenylthio group , 4-t-butylphenylthio group, 2-methoxyphenylthio group, 4-iso-propylphenylthio group, tolylthio group, naphthylthio group, ferrocenylthio group, cobaltosenylthio group, nickeloselenyl C6-C18 arylthio groups, such as a group, an octamethyl ferrocenylthio group, an octamethyl cobaltosenylthio group, and an octamethyl nickel lozenylthio group, are mentioned.

Moreover, as an example of the substituted or unsubstituted heteroarylthio group of R <^1> -R <^16> which is an arylthio group which has an oxygen atom, a substituted or unsubstituted sulfur atom, and a substituted or unsubstituted nitrogen atom between carbon-carbon atoms, the hetero enumerated above Heteroarylthio group which an aryl group couple | bonds with an oxygen atom is mentioned.

As an example of the substituted or unsubstituted alkenylthio group of R ¹ to R ^{16, as} the alkenylthio group which may have the same substituent as the alkyl groups listed above, Preferably a vinylthio group, a propenylthio group, a 1-butenylthio group, iso-butenylthio group, 1-pentenylthio group, 2-pentenylthio group, 2-methyl-1-butenylthio group, 3-methyl-1-butenylthio group, 2-methyl-2-butenylthio group, cyclopenta Dienylthio group, 2,2-dicyanovinylthio group, 2-cyano-2-methylcarboxyvinylthio group, 2-cyano-2-methylsulfonvinylthio group, styrylthio group, 4-phenyl-2 C2-C10 alkenylthio groups, such as a butenylthio group and a cinnamil alkoxy group, are mentioned.

Moreover, the hydrocarbon thio group in which the carbon atom couple | bonded directly with the sulfur atom which couple | bonded directly with the azaanulene ring is substituted by the oxo group is mentioned as a substituted hydrocarbon thi group represented by R <^1> -R <^16> . As a specific example, Substituted or unsubstituted acylthio group; Substituted or unsubstituted hydrocarbon oxycarbonylthio groups such as alkoxycarbonylthio group, aralkyloxycarbonylthio group, aryloxycarbonylthio group and alkenyloxycarbonylthio group; Substituted or unsubstituted hydrocarbon aminocarbonylthio groups, such as a mono substituted aminocarbonylthio group and a di-substituted aminocarbonylthio group, etc. are mentioned.

As an example of the substituted or unsubstituted acylthio group of R <^1> -R <^16> , As an acylthio group which may have the same substituent as the above-mentioned alkyl group, Preferably it is a formylthio group, methylcarbonylthio group, ethylcarbonylthio group , n-propylcarbonylthio group, iso-propylcarbonylthio group, n-butylcarbonylthio group, iso-butylcarbonylthio group, sec-butylcarbonylthio group, t-butylcarbonylthio group, n -Pentylcarbonylthio group, iso-pentylcarbonylthio group, neopentylcarbonylthio group, 2-methylbutylcarbonylthio group, benzoylthio group, methylbenzoylthio group, ethylbenzoylthio group, tolylcarbonylthio group , Propylbenzoylthio group, 4-t-butylbenzoylthio group, nitrobenzylcarbonylthio group, 3-butoxy-2-naphthoylthio group, cinnamoylthio group, ferrocenecarbonylthio group, 1-methyl ferrocene- C1-C15 acylthio groups, such as a 1'-carbonylthio group, are mentioned.

As an example of the substituted or unsubstituted alkoxycarbonylthio group of R <^1> -R <^16> , As an alkoxycarbonylthio group which may have the same substituent as the above-mentioned alkyl group, Preferably a methoxycarbonylthio group and an ethoxy carbonbo Nylthio group, n-propoxycarbonylthio group, iso-propoxycarbonylthio group, n-butoxycarbonylthio group, iso-butoxycarbonylthio group, sec-butoxycarbonylthio group, t- Butoxycarbonylthio group, n-pentoxycarbonylthio group, iso-pentoxycarbonylthio group, neopentoxycarbonylthio group, 2-pentoxycarbonylthio group, 2-ethylhexyloxycarbonyl thi Ogi, 3,5,5-trimethylhexyloxycarbonylthio group, dekaryloxycarbonylthio group, cyclohexyloxycarbonylthio group, chloroethoxycarbonylthio group, hydroxymethoxycarbonylthio group, and hydroxide Alkoxycarbonyl of 2 to 11 carbon atoms such as oxyethoxycarbonylthio group Import;

Methoxy methoxycarbonylthio group, methoxyethoxycarbonylthio group, ethoxyethoxycarbonylthio group, propoxyoxycarbonylthio group, butoxyethoxycarbonylthio group, pentoxyethoxycarbon Bonylthio group, hexyloxyethoxycarbonylthio group, butoxybutoxycarbonylthio group, hexyloxybutoxycarbonylthio group, hydroxymethoxymethoxycarbonylthio group, hydroxyethoxyethoxycarbon An alkoxycarbonylthio group having 3 to 11 carbon atoms in which alkylthio groups such as a vinylyl group are substituted;

Methoxy methoxy methoxycarbonylthio group, methoxyethoxyethoxycarbonylthio group, ethoxyethoxyethoxycarbonylthio group, propoxyethoxy ethoxycarbonylthio group, butoxyethoxyethoxy An alkoxycarbonylthio group having 4 to 11 carbon atoms in which an alkoxyalkoxy group such as a carbonylthio group, a pentoxyethoxyethoxycarbonylthio group and a hexyloxyethoxyethoxycarbonylthio group is substituted;

Ferrocenyl methoxycarbonylthio group, ferrocenyl ethoxycarbonylthio group, ferrocenyl propoxycarbonylthio group, ferrocenyl butoxycarbonylthio group, ferrocenyl pentyl oxycarbonylthio group, ferrocenyl hexyloxyka A carbonylthio group, a ferrocenylheptyloxycarbonylthio group, a ferrocenyl octyloxycarbonylthio group, a ferrocenyl nonyloxycarbonylthio group, a ferrocenyldecyloxycarbonylthio group,

Cobaltosenylmethoxycarbonylthio group, cobaltosenylethoxycarbonylthio group,

Nickellocenylmethoxycarbonylthio group, nickellocenylethoxycarbonylthio group,

Dichloro titanosenyl methoxycarbonylthio group, trichloro titanium cyclopentadienyl methoxycarbonylthio group, bis (trifluoromethane sulfonate) titanocene methoxycarbonylthio group, dichloro zirconocenyl methoxycarbonyl thi Ogi, dimethyl zirconocenyl methoxycarbonylthio group, diethoxy zirconocenyl methoxycarbonylthio group, bis (cyclopentadienyl) chrome methoxycarbonylthio group, bis (cyclopentadienyl) dichloro hafnium me Methoxycarbonylthio group, bis (cyclopentadienyl) dichloroniobmethoxycarbonylthio group, bis (cyclopentadienyl) ruthenium methoxycarbonylthio group, bis (cyclopentadienyl) vanadium methoxycarbonylti Carbon substituted with metallocenyl groups, such as group, bis (cyclopentadienyl) dichlorovanadium methoxycarbonylthio group, and bis (cyclopentadienyl) osmium methoxycarbonylthio group And the like alkoxy carbonyl nilti coming of 11-20.

As an example of the substituted or unsubstituted aralkyloxycarbonylthio group of R ¹ to R ¹⁶ , an aralkyloxycarbonylthio group which may have the same substituent as the above-mentioned alkyl group, preferably a benzyloxycarbonylthio group, Nitrobenzyloxycarbonylthio group, cyanobenzyloxycarbonylthio group, hydroxybenzyloxycarbonylthio group, methylbenzyloxycarbonylthio group, trifluoromethylbenzyloxycarbonylthio group, naphthyl methoxycarbono Nylthio group, nitronaphthyl methoxycarbonylthio group, cyanonaphthyl methoxycarbonylthio group, hydroxy naphthyl methoxycarbonylthio group, methylnaphthyl methoxycarbonylthio group, trifluoromethylnaphthyl methoxycarbon And aralkyloxycarbonylthio groups having 8 to 16 carbon atoms, such as a silylthio group and a fluorene-9-ylethoxycarbonylthio group.

As an example of the substituted or unsubstituted aryloxycarbonylthio group of R ¹ to R ¹⁶ , an aryloxycarbonylthio group which may have the same substituent as the above-mentioned aryl group, preferably a phenoxycarbonylthio group, 2-methyl Phenoxycarbonylthio group, 4-methylphenoxycarbonylthio group, 4-t-butylphenoxycarbonylthio group, 2-methoxyphenoxycarbonylthio group, 4-iso-propylphenoxycarbonylthio group, naphthoxycarbon Carbonylthio group, ferrocenyloxycarbonylthio group, cobaltosenyloxycarbonylthio group, nickellocenyloxycarbonylthio group, zirconosenyloxycarbonylthio group, octamethylferrocenyloxycarbonylthio group, octa And aryloxycarbonylthio groups having 7 to 11 carbon atoms, such as a methyl cobaltosenyloxycarbonylthio group, an octamethylnickelocenyloxycarbonylthio group, and an octamethyl zirconocenyloxycarbonyloxy group.

As an example of the substituted or unsubstituted alkenyloxycarbonylthio group of R <^1> -R <^16> , it is an alkenyloxycarbonylthio group which may have a substituent same as the above-mentioned alkyl group, Preferably it is a vinyloxycarbonylthio group, Propenyloxycarbonylthio group, 1-butenyloxycarbonylthio group, iso-butenyloxycarbonylthio group, 1-pentenyloxycarbonylthio group, 2-pentenyloxycarbonylthio group, cyclopenta Dienyloxycarbonylthio group, 2-methyl-1-butenyloxycarbonylthio group, 3-methyl-1-butenyloxycarbonylthio group, 2-methyl-2-butenyloxycarbonylthio group, 2,2-dicyanovinyloxycarbonylthio group, 2-cyano-2-methylcarboxyvinyloxycarbonylthio group, 2-cyano-2-methylsulfonvinyloxycarbonylthio group, styryloxycarbon Alkenyloxycarbonylthio groups having 3 to 11 carbon atoms such as a carbonylthio group and a 4-phenyl-2-butenyloxycarbonylthio group Can be mentioned.

As an example of the monosubstituted aminocarbonylthio group of R <^1> -R <^{16>, it} is a monosubstituted aminocarbonylthio group which may have the same substituent as the above-mentioned alkyl group, Preferably methylaminocarbonylthio group and ethylaminocarbono Nylthio group, propylaminocarbonylthio group, butylaminocarbonylthio group, pentylaminocarbonylthio group, hexylaminocarbonylthio group, heptylaminocarbonylthio group, octylaminocarbonylthio group, (2-ethylhexyl C2-C11, such as an aminocarbonylthio group, a cyclohexylamino carbonylthio group, a (3,5,5-trimethylhexyl) aminocarbonylthio group, a nonylaminocarbonylthio group, a decylaminocarbonylthio group, etc. Monoalkylaminocarbonylthio group;

Benzylaminocarbonylthio group, phenethylaminocarbonylthio group, (3-phenylpropylaminocarbonylthio group, (4-ethylbenzyl) aminocarbonylthio group, (4-isopropylbenzyl) aminocarbonylthio group , (4-methylbenzyl) aminocarbonylthio group, (4-ethylbenzyl) aminocarbonylthio group, (4-allylbenzyl) aminocarbonylthio group, [4- (2-cyanoethyl) benzyl] amino Monoaralkylaminocarbonylthio groups having 8 to 1 carbon atoms such as a carbonylthio group and a [4- (2-acetoxyethyl) benzyl] aminocarbonylthio group;

Anilinocarbonylthio group, naphthylaminocarbonylthio group, toluidinocarbonylthio group, xyldinocarbonylthio group, ethylanilinocarbonylthio group, isopropylanilinocarbonylthio group, methoxy Anilinocarbonylthio group, ethoxyanilinocarbonylthio group, chloroanilinocarbonylthio group, acetylanilinocarbonylthio group, methoxycarbonylanilinocarbonylthio group, ethoxycarbonylanilinocarbon Monoarylaminocarbonylthio groups having 7 to 11 carbon atoms such as a carbonylthio group, propoxycarbonylanilinocarbonylthio group, 4-methylanilinocarbonylthio group, and 4-ethylanilinocarbonylthio group;

Vinylaminocarbonylthio group, allylaminocarbonylthio group, butenylaminocarbonylthio group, pentenylaminocarbonylthio group, hexenylaminocarbonylthio group, cyclohexenylaminocarbonylthio group, octadienyl And C3-C11 monoalkenylaminocarbonylthio groups, such as an aminocarbonylthio group and an adamantenylaminocarbonylthio group, etc. are mentioned.

As an example of the di-substituted aminocarbonylthio group of R <^1> -R <^{16>, It} is a di-substituted aminocarbonylthio group which may have the same substituent as the above-mentioned alkyl group, Preferably it is a dimethylaminocarbonylthio group and diethylaminocarbon Carbonylthio group, methylethylaminocarbonylthio group, dipropylaminocarbonylthio group, dibutylaminocarbonylthio group, di-n-hexylaminocarbonylthio group, dicyclohexylaminocarbonylthio group, dioctyl Aminocarbonylthio group, pyrrolidinocarbonylthio group, piperidinocarbonylthio group, morpholinocarbonylthio group, bis (methoxyethyl) aminocarbonylthio group, bis (ethoxyethyl) aminocarbon Nylthio group, bis (propoxyethyl) aminocarbonylthio group, bis (butoxyethyl) aminocarbonylthio group, di (acetyloxyethyl) aminocarbonylthio group, di (hydroxyethyl) aminocarbon Thio, N- ethyl -N- (2- cyanoethyl) amino carbonyloxy nilti come, di (propionyloxy ethyl) amino carbonyloxy nilti dialkylamino of 3-17 carbon atoms, such as coming-amino carbonyloxy nilti come;

C3-C21 dicarbons, such as a dibenzylaminocarbonylthio group, a diphenethylaminocarbonylthio group, a bis (4-ethylbenzyl) aminocarbonylthio group, and a bis (4-isopropylbenzyl) aminocarbonylthio group Aralkylaminocarbonylthio group;

C13-C15 diarylaminocarbonylthio group, such as a diphenylaminocarbonylthio group, a ditolylaminocarbonylthio group, and N-phenyl-N-tolylaminocarbonylthio group;

Divinylaminocarbonylthio group, diallylaminocarbonylthio group, dibutenylaminocarbonylthio group, dipentenylaminocarbonylthio group, dihexenylaminocarbonylthio group, N-vinyl-N-allylaminocarbon C5-C13 dialkylaminocarbonylthio groups, such as a ylthio group;

N-phenyl-N-allylaminocarbonylthio group, N- (2-acetyloxyethyl) -N-ethylaminocarbonylthio group, N-tolyl-N-methylaminocarbonylthio group, N-vinyl-N C4-C11 di-substituted aminocar having a substituent selected from a substituted or unsubstituted alkyl group, aralkyl group, aryl group, alkenyl group, such as -methylaminocarbonylthio group and N-benzyl-N-allylaminocarbonylthio group A carbonylthio group is mentioned.

Specific examples of the substituted or unsubstituted amino group represented by R ¹ to R ¹⁶ include an unsubstituted amino group; And mono-substituted amino groups and di-substituted amino groups which may have an oxygen atom, a substituted or unsubstituted sulfur atom, or a substituted or unsubstituted nitrogen atom between carbon-carbon atoms.

As an example of the mono substituted amino group of R <^1> -R <^16> , As a mono substituted amino group which may have the same substituent as the above-mentioned alkyl group, Preferably, methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group , Isobutylamino group, tert-butylamino group, sec-butylamino group, n-pentylamino group, isopentylamino group, tert-pentylamino group, sec-pentylamino group, cyclopentylamino group, n-hexylamino group, 1-methylpentylamino group, 2 -Methylpentylamino group, 3-methylpentylamino group, 4-methylpentylamino group, 1,1-dimethylbutylamino group, 1,2-dimethylbutylamino group, 1,3-dimethylbutylamino group, 2,3-dimethylbutylamino group, 1 , 1,2-trimethylpropylamino group, 1,2,2-trimethylpropylamino group, 1-ethylbutylamino group, 2-ethylbutylamino group, 1-ethyl-2-methylpropylamino group, cyclohexylamino group, methylcyclopentyl Mino group, n-heptylamino group, 1-methylhexylamino group, 2-methylhexylamino group, 3-methylhexylamino group, 4-methylhexylamino group, 5-methylhexylamino group, dimethylpentylamino group, 1-ethylpentylamino group, 2- Ethylpentylamino group, 3-ethylpentylamino group, trimethylbutylamino group, 1-ethyl-1-methylbutylamino group, 1-ethyl-2-methylbutylamino group, 1-ethyl-3-methylbutylamino group, 2-ethyl-1- Methylbutylamino group, 2-ethyl-3-methylbutylamino group, 1-n-propylbutylamino group, 1-isopropylbutylamino group, 1-isopropyl-2-methylpropylamino group, methylcyclohexylamino group, n-octylamino group, 1-methylheptylamino group, 2-methylheptylamino group, 3-methylheptylamino group, 4-methylheptylamino group, 5-methylheptylamino group, 6-methylheptylamino group, dimethylhexylamino group, 1-ethylhexylamino group, 2-ethylhexyl Amino group, 3-ethylhexylamino group, 4-ethylhexylamino group, 1-n-pro Pentylamino group, 2-n-propylpentylamino group, 1-isopropylpentylamino group, 2-isopropylpentylamino group, 1-ethyl-1-methylpentylamino group, l-ethyl-2-methylpentylamino group, 1-ethyl-3 -Methylpentylamino group, 1-ethyl-4-methylpentylamino group, 2-ethyl-1-methylpentylamino group, 2-ethyl-2-methylpentylamino group, 2-ethyl-3-methylpentylamino group, 2-ethyl-4 -Methylpentylamino group, 3-ethyl-1-methylpentylamino group, 3-ethyl-2-methylpentylamino group, 3-ethyl-3-methylpentylamino group, 3-ethyl-4-methylpentylamino group, trimethylpentylamino group, 1 -n-butylbutylamino group, 1-isobutylbutylamino group, 1-sec-butylbutylamino group, 1-tert-butylbutylamino group, 2-tert-butylbutylamino group, 1-n-propyl-1-methylbutylamino group, 1-n-propyl-2-methylbutylamino group, 1-n-propyl-3-methylbutylamino group, 1-isopropyl-1-methylbutylamino group, 1-isopropyl-2-methylbutylamino group, 1-isopro Phil-3-methylbutylamino group, 1, 1-diethylbutylamino group, 1, 2-diethylbutylamino group, 1-ethyl-1,2-dimethylbutylamino group, 1-ethyl-1,3-dimethylbutylamino group, 1-ethyl-2,3-dimethylbutylamino group, 2-ethyl-1,1-dimethylbutylamino group, 2-ethyl-1,2-dimethylbutylamino group, 2-ethyl-1,3-dimethylbutylamino group, 2- Ethyl-2,3-dimethylbutylamino group, 1,1,3,3-tetramethylbutylamino group, 1,2-dimethylcyclohexylamino group, 1,3-dimethylcyclohexylamino group, 1,4-dimethylcyclohexylamino group, Ethylcyclohexylamino group, n-nonylamino group, 3,5,5-trimethylhexylamino group, n-decylamino group, n-undecylamino group, n-dodecylamino group, 1-adamantylamino group, n-pentadecylamino group, etc. Linear, branched or cyclic unsubstituted monoalkylamino group having 1 to 15 carbon atoms;

Methoxymethylamino group, methoxyethylamino group, ethoxyethylamino group, n-propoxyethylamino group, isopropoxyethylamino group, n-butoxyethylamino group, isobutoxyethylamino group, tert-butoxyethylamino group, sec-part Methoxyethylamino group, n-pentyloxyethylamino group, isopentyloxyethylamino group, tert-pentyloxyethylamino group, sec-pentyloxyethylamino group, cyclopentyloxyethylamino group, n-hexyloxyethylamino group, ethylcyclohexyloxyethylamino group , n-nonyloxyethylamino group, (3,5,5-trimethylhexyloxy) ethylamino group, (3,5,5-trimethylhexyloxy) butylamino group, n-decyloxyethylamino group, n-undecyloxy Ethylamino group, n-dodecyloxyethylamino group, 3-methoxypropylamino group, 3-ethoxypropylamino group, 3- (n-propoxy) propylamino group, 2-isopropoxypropylamino group, 2-methoxybutylamino group , 2-ethoxy Butyl group, 2- (n- propoxy) butyl group, 4-isopropoxy-butyl group, a big reel oxyethyl group, an adamantyloxy ethyl monoalkylamino group of carbon atoms from 2 to 15 substituted with an alkoxy group and the like;

Methoxymethoxymethylamino group, ethoxymethoxymethylamino group, propoxymethoxymethylamino group, butoxymethoxymethylamino group, methoxyethoxymethylamino group, ethoxyethoxymethylamino group, propoxyethoxymethylamino group, part Methoxyethoxymethylamino group, methoxypropoxymethylamino group, ethoxypropoxymethylamino group, propoxypropoxymethylamino group, butoxypropoxymethylamino group, methoxybutoxymethylamino group, ethoxybutoxymethylamino group, propoxy Butoxymethylamino group, butoxybutoxymethylamino group, methoxymethoxyethylamino group, ethoxymethoxyethylamino group, propoxymethoxyethylamino group, butoxymethoxyethylamino group, methoxyethoxyethylamino group, ethoxye Methoxyethylamino group, propoxyoxyethylamino group, butoxyethoxyethylamino group, methoxypropoxyethylamino group, ethoxypropoxy Cethylamino group, propoxypropoxyethylamino group, butoxypropoxyethylamino group, methoxybutoxyethylamino group, ethoxybutoxyethylamino group, propoxybutoxyethylamino group, butoxybutoxyethylamino group, methoxymethoxy Propylamino group, ethoxymethoxypropylamino group, propoxymethoxypropylamino group, butoxymethoxypropylamino group, methoxyethoxypropylamino group, ethoxyethoxypropylamino group, propoxyethoxypropylamino group, butoxyethoxypropyl Amino group, methoxypropoxypropylamino group, ethoxypropoxypropylamino group, propoxypropoxypropylamino group, butoxypropoxypropylamino group, methoxybutoxypropylamino group, ethoxybutoxypropylamino group, propoxybutoxypropylamino group , Butoxybutoxypropylamino group, methoxymethoxybutylamino group, ethoxymethoxy Butylamino group, propoxymethoxybutylamino group, butoxymethoxybutylamino group, methoxyethoxybutylamino group, ethoxyethoxybutylamino group, propoxyethoxybutylamino group, butoxyethoxybutoxy group, methoxypropoxybutyl Amino group, ethoxypropoxybutylamino group, propoxypropoxybutylamino group, butoxypropoxybutylamino group, methoxybutoxybutylamino group, ethoxybutoxybutylamino group, propoxybutoxybutylamino group, butoxybutoxybutylamino group , (4-ethylcyclohexyloxy) ethoxyethylamino group, (2-ethyl-1-hexyloxy) ethoxypropylamino group, [4- (3,5,5-trimethylhexyloxy) butoxy] ethyl Linear, branched or cyclic monoalkylamino groups having 3 to 15 carbon atoms substituted with alkoxyalkoxy groups such as amino groups;

Alkoxycarbonyl groups, such as a methoxycarbonylmethylamino group, an ethoxycarbonylmethylamino group, n-propoxycarbonylmethylamino group, isopropoxycarbonylmethylamino group, (4'-ethylcyclohexyloxy) carbonylmethylamino group, etc. Substituted monoalkylamino group having 3 to 10 carbon atoms;

C3-C10 monoalkylamino group substituted by the acyl group, such as an acetylmethylamino group, an ethylcarbonylmethylamino group, an octylcarbonylmethylamino group, and a phenacylamino group;

Monoalkylamino groups having 3 to 10 carbon atoms substituted with acylamino groups such as acetyloxymethylamino group, acetyloxyethylamino group, acetyloxyhexylamino group and butanoyloxycyclohexylamino group;

Methylaminomethylamino group, 2-methylaminoethylamino group, 2- (2-methylaminoethoxy) ethylamino group, 4-methylaminobutylamino group, 1-methylaminopropan-2-ylamino group, 3-methylaminopropylamino group, 2-methylamino-2-methylpropylamino group, 2-ethylaminoethylamino group, 2- (2-ethylaminoethoxy) ethylamino group, 3-ethylaminopropylamino group, 1-ethylaminopropylamino group, 2-isopropylamino C2-C10 monoalkylamino group substituted by monoalkylamino groups, such as an ethylamino group, 2- (n-butylamino) ethylamino group, 3- (n-hexylamino) propylamino group, and 4- (cyclohexylamino) butylamino group ;

Alkylamino monoalkylamino groups, such as a methylamino methoxymethylamino group, methylaminoethoxyethylamino group, methylaminoethoxypropylamino group, ethylaminoethoxypropylamino group, and 4- (2'-isobutylaminopropoxy) butylamino group Substituted monoalkylamino group having 3 to 10 carbon atoms;

Dimethylaminomethylamino group, 2-dimethylaminoethylamino group, 2- (2-dimethylaminoethoxy) ethylamino group, 4-dimethylaminobutylamino group, 1-dimethylaminopropan-2-ylamino group, 3-dimethylaminopropylamino group, 2-dimethylamino-2-methylpropylamino group, 2-diethylaminoethylamino group, 2- (2-diethylaminoethoxy) ethylamino group, 3-diethylaminopropylamino group, 1-diethylaminopropylamino group, 2 Substituted with dimonoalkylamino groups such as diisopropylaminoethylamino group, 2- (di-n-butylamino) ethylamino group, 2-piperidylethylamino group, and 3- (di-n-hexylamino) propylamino group Monoalkylamino group having 3 to 15 carbon atoms;

Dialkylamino monos such as dimethylaminomethoxymethylamino group, dimethylaminoethoxyethylamino group, dimethylaminoethoxypropylamino group, diethylaminoethoxypropylamino group and 4- (2'-diisobutylaminopropoxy) butylamino group C4-C15 monoalkylamino group substituted by the alkylamino group;

Methylthiomethylamino group, 2-methylthioethylamino group, 2-ethylthioethylamino group, 2-n-propylthioethylamino group, 2-isopropylthioethylamino group, 2-n-butylthioethylamino group, 2-isobutylthio C2-C15 monoalkylamino group substituted by monoalkylamino groups, such as an ethylamino group and a (3,5,5-trimethylhexylthio) hexylamino group;

Monoalkylamino groups, such as methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, n-butylamino group, iso-butylamino group, sec-butylamino group, t-butylamino group, n-pentylamino group, etc. more preferably , iso-pentylamino group, neopentylamino group, 2-methylbutylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group, 3,5,5-trimethylhexylamino group, dekarylamino group Monoalkylamino groups having 1 to 10 carbon atoms such as methoxyethylamino group, ethoxyethylamino group, methoxyethoxyethylamino group, ethoxyethoxyethylamino group and n-decylamino group;

Benzylamino group, phenethylamino group, (3-phenylpropyl) amino group, (4-ethylbenzyl) amino group, (4-isopropylbenzyl) amino group, (4-methylbenzyl) amino group, (4-ethylbenzyl) amino group, (4 Monoaralkylamino groups having 7 to 10 carbon atoms such as allyl benzyl) amino group, [4- (2-cyanoethyl) benzyl] amino group, and [4- (2-acetoxyethyl) benzyl] amino group;

Anilino group, naphthylamino group, toludino group, xylino group, ethylanilino group, isopropylanilino group, methoxyanilino group, ethoxyanilino group, chloroanilino group, acetylanilino group , Methoxycarbonylanilino group, ethoxycarbonylanilino group, propoxycarbonylanilino group, 4-methylanilino group, 4-ethylanilino group, ferrocenylamino group, cobaltosenylamino group, nickelo C6-C10 monoarylamino groups, such as a senylamino group, a zirconocenylamino group, an octamethyl ferrocenylamino group, an octamethyl cobaltosenylamino group, an octamethyl nickellocenylamino group, an octamethyl zirconocenylamino group;

Monoalkenylamino groups having 2 to 10 carbon atoms such as vinylamino group, allylamino group, butenylamino group, pentenylamino group, hexenylamino group, cyclohexenylamino group, cyclopentadienylamino group, octadienylamino group, and adamantenylamino group;

Formylamino group, methylcarbonylamino group, ethylcarbonylamino group, n-propylcarbonylamino group, iso-propylcarbonylamino group, n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t -Butylcarbonylamino group, n-pentylcarbonylamino group, iso-pentylcarbonylamino group, neopentylcarbonylamino group, 2-methylbutylcarbonylamino group, benzoylamino group, methylbenzoylamino group, ethylbenzoylamino group, tolylcarbonylamino group, Propylbenzoylamino group, 4-t-butylbenzoylamino group, nitrobenzylcarbonylamino group, 3-butoxy-2-naphthoylamino group, cinnamoylamino group, ferrocenecarbonylamino group, 1-methylferrocene-1'-carbonylamino group, Acylamino groups having 1 to 16 carbon atoms such as cobaltocenecarbonylamino group and nickellocenecarbonylamino group; Mono substituted amino groups, such as these, are mentioned.

As an example of the di substituted amino group of R <^1> -R <^16> , As a di-substituted amino group which may have the same substituent as the above-mentioned alkyl group, Preferably it is a dimethylamino group, a diethylamino group, a di (n-propyl) amino group, and di (isopropyl). ) Amino group, di (n-butyl) amino group, di (isobutyl) amino group, di (tert-butyl) amino group, di (sec-butyl) amino group, di (n-pentyl) amino group, di (isopentyl) amino group, Di (tert-pentyl) amino group, di (sec-pentyl) amino group, di (cyclopentyl) amino group, di (n-hexyl) amino group, di (1-methylpentyl) amino group, di (2-methylpentyl) amino group, di (3-methylpentyl) amino group, di (4-methylpentyl) amino group, di (1,1-dimethylbutyl) amino group, di (1,2-dimethylbutyl) amino group, di (1,3-dimethylbutyl) amino group, Di (2,3-dimethylbutyl) amino group, di (1,1,2-trimethylpropyl) amino group, di (1,2,2-trimethylpropyl) amino group, di (1-ethylbutyl) amino group, (2-ethylbutyl) amino group, di (1-ethyl-2-methylpropyl) amino group, di (cyclohexyl) amino group, di (methylcyclopentyl) amino group, di (n-heptyl) amino group, di (1-methylhexyl) ) Amino group, di (2-methylhexyl) amino group, di (3-methylhexyl) amino group, di (4-methylhexyl) amino group, di (5-methylhexyl) amino group, di (dimethylpentyl) amino group, di (1- Ethylpentyl) amino group, di (2-ethylpentyl) amino group, di (3-ethylpentyl) amino group, di (trimethylbutyl) amino group, di (1-ethyl-1-methylbutyl) amino group, di (1-ethyl-2 -Methylbutyl) amino group, di (1-ethyl-3-methylbutyl) amino group, di (2-ethyl-1-methylbutyl) amino group, di (2-ethyl-3-methylbutyl) amino group, di (1-n -Propylbutyl) amino group, di (1-isopropylbutyl) amino group, di (1-isopropyl-2-methylpropyl) amino group, di (methylcyclohexyl) amino group, di (n-octyl) amino group, di (1- Methylheptyl) amino group, di (2-methylheptyl) amino group, di (3-meth Heptyl) amino group, di (4-methylheptyl) amino group, di (5-methylheptyl) amino group, di (6-methylheptyl) amino group, di (dimethylhexyl) amino group, di (1-ethylhexyl) amino group, di (2 -Ethylhexyl) amino group, di (3-ethylhexyl) amino group, di (4-ethylhexyl) amino group, di (1-n-propylpentyl) amino group, di (2-n-propylpentyl) amino group, di (1- Isopropylpentyl) amino group, di (2-isopropylpentyl) amino group, di (1-ethyl-1-methylpentyl) amino group, di (1-ethyl-2-methylpentyl) amino group, di (1-ethyl-3- Methylpentyl) amino group, di (1-ethyl-4-methylpentyl) amino group, di (2-ethyl-1-methylpentyl) amino group, di (2-ethyl-2-methylpentyl) amino group, di (2-ethyl- 3-methylpentyl) amino group, di (2-ethyl-4-methylpentyl) amino group, di (3-ethyl-1-methylpentyl) amino group, di (3-ethyl-2-methylpentyl) amino group, di (3- Ethyl-3-methylpentyl) amino group, di (3-ethyl-4-methylpentyl) amino group, di (trimethylpentyl) amino group, di (1-n-part Butyl) amino group, di (1-isobutylbutyl) amino group, di (1-sec-butylbutyl) amino group, di (1-tert-butylbutyl) amino group, di (2-tert-butylbutyl) amino group, di (1 -n-propyl-1-methylbutyl) amino group, di (1-n-propyl-2-methylbutyl) amino group, di (1-n-propyl-3-methylbutyl) amino group, di (1-isopropyl-1 -Methylbutyl) amino group, di (1-isopropyl-2-methylbutyl) amino group, di (1-isopropyl-3-methylbutyl) amino group, di (1,1-diethylbutyl) amino group, di (1, 2-diethylbutyl) amino group, di (l-ethyl-1,2-dimethylbutyl) amino group, di (1-ethyl-1,3-dimethylbutyl) amino group, di (1-ethyl-2,3-dimethylbutyl ) Amino group, di (2-ethyl-1,1-dimethylbutyl) amino group, di (2-ethyl-1,2-dimethylbutyl) amino group, di (2-ethyl-1,3-dimethylbutyl) amino group, di ( 2-ethyl-2,3-dimethylbutyl) amino group, di (1,1,3,3-tetramethylbutyl) amino group, di (1,2-dimethylcyclohexyl) amino group, di (1,3-dimethylcyclohex ) Amino group, di (1,4-dimethylcyclohexyl) amino group, di (ethylcyclohexyl) amino group, di (n-nonyl) amino group, di (3,5,5-trimethylhexyl) amino group, di (n-decyl) Straight chain, branched or ring of 1 to 15 carbon atoms such as amino group, di (n-undecyl) amino group, di (n-dodecyl) amino group, di (1-adamantyl) amino group and di (n-pentadecyl) amino group Unsubstituted dialkylamino group of the type;

Di (methoxymethyl) amino group, di (methoxyethyl) amino group, di (ethoxyethyl) amino group, di (n-propoxyethyl) amino group, di (isopropoxyethyl) amino group, di (n-butoxyethyl ) Amino group, di (isobutoxyethyl) amino group, di (tert-butoxyethyl) amino group, di (sec-butoxyethyl) amino group, di (n-pentyloxyethyl) amino group, di (isopentyloxyethyl) amino group, Di (tert-pentyloxyethyl) amino group, di (sec-pentyloxyethyl) amino group, di (cyclopentyloxyethyl) amino group, di (n-hexyloxyethyl) amino group, di (ethylcyclohexyloxyethyl) amino group, di (n-nonyloxyethyl) amino group, di [(3,5,5-trimethylhexyloxy) ethyl] amino group, di [(3,5,5-trimethylhexyloxy) butyl] amino group, di (n-decyl Oxyethyl) amino group, di (n-undecyloxyethyl) amino group, di (n-dodecyloxyethyl) amino group, di (3-methoxypropyl) amino group, di (3-ethoxypropyl) amino group, di [3 -( n-propoxy) propyl] amino group, di (2-isopropoxypropyl) amino group, di (2-methoxybutyl) amino group, di (2-ethoxybutyl) amino group, di [2- (n-propoxy) C2-C15 dialkylamino group substituted by the alkoxy group, such as a butyl] amino group, a di (4-isopropoxy butyl) amino group, a di (decarylyl ethyl ethyl) amino group, and a di (adamantyloxy ethyl) amino group;

(Methoxymethoxymethyl) amino group, di (ethoxymethoxymethyl) amino group, di (propoxymethoxymethyl) amino group, di (butoxymethoxymethyl) amino group, di (methoxyethoxymethyl) amino group, di (Ethoxyethoxymethyl) amino group, di (propoxyethoxymethyl) amino group, di (butoxyethoxymethyl) amino group, di (methoxypropoxymethyl) amino group, di (ethoxypropoxymethyl) amino group, di (Propoxypropoxymethyl) amino group, di (butoxypropoxymethyl) amino group, di (methoxybutoxymethyl) amino group, di (ethoxybutoxymethyl) amino group, di (propoxybutoxymethyl) amino group, di (Butoxybutoxymethyl) amino group, di (methoxymethoxyethyl) amino group, di (ethoxymethoxyethyl) amino group, di (propoxymethoxyethyl) amino group, di (butoxymethoxyethyl) amino group, di (Methoxyethoxyethyl) amino group, di (ethoxyethoxyethyl) amino group, di (propoxyethoxy ) Amino group, di (butoxyethoxyethyl) amino group, di (methoxypropoxyethyl) amino group, di (ethoxypropoxyethyl) amino group, di (propoxypropoxyethyl) amino group, di (butoxypropoxyethyl ) Amino group, di (methoxybutoxyethyl) amino group, di (ethoxybutoxyethyl) amino group, di (propoxybutoxyethyl) amino group, di (butoxybutoxyethyl) amino group, di (methoxymethoxypropyl ) Amino group, di (ethoxymethoxypropyl) amino group, di (propoxymethoxypropyl) amino group, di (butoxymethoxypropyl) amino group, di (methoxyethoxypropyl) amino group, di (ethoxyethoxypropyl ) Amino group, di (propoxyethoxypropyl) amino group, di (butoxyethoxypropyl) amino group, di (methoxypropoxypropyl) amino group, di (ethoxypropoxypropyl) amino group, di (propoxypropoxypropyl ) Amino group, di (butoxypropoxypropyl) amino group, di ( Methoxybutoxypropyl) amino group, di (ethoxybutoxypropyl) amino group, di (propoxybutoxypropyl) amino group, di (butoxybutoxypropyl) amino group, di (methoxymethoxybutyl) amino group, di (e) Methoxymethoxybutyl) amino group, di (propoxymethoxybutyl) amino group, di (butoxymethoxybutyl) amino group, di (methoxyethoxybutyl) amino group, di (ethoxyethoxybutyl) amino group, di (pro Foxoxyoxybutyl) amino group, di (butoxyethoxybutoxy group, methoxypropoxybutyl) amino group, di (ethoxypropoxybutyl) amino group, di (propoxypropoxybutyl) amino group, di (butoxypropoxy Butyl) amino group, di (methoxybutoxybutyl) amino group, di (ethoxybutoxybutyl) amino group, di (propoxybutoxybutyl) amino group, di (butoxybutoxybutyl) amino group, di [(4-ethyl Cyclohexyloxy) ethoxyethyl] amino group, di [(2-ethyl-1-hexyloxy) ethoxypropyl] a Group, a di {[4- (3,5,5-trimethyl-hexyloxy) butoxy] ethyl} amino group and the like alkoxy groups of the alkoxy-substituted straight-chain, branched, or 3 to 15 carbon atoms, a dialkylamino group of the cyclic;

Di (methoxycarbonylmethyl) amino group, di (ethoxycarbonylmethyl) amino group, di (n-propoxycarbonylmethyl) amino group, di (isopropoxycarbonylmethyl) amino group, di [(4'-ethyl C3-C10 dialkylamino group substituted by the alkoxycarbonyl group, such as cyclohexyloxy) carbonylmethyl] amino group;

C3-C10 dialkylamino group substituted by the acyl group, such as a di (acetylmethyl) amino group, a di (ethylcarbonylmethyl) amino group, a di (octylcarbonylmethyl) amino group, and a di (phenacyl) amino group;

C3-C10 dialkylamino group substituted by the acylamino group, such as a di (acetyloxymethyl) amino group, a di (acetyloxyethyl) amino group, a di (acetyloxyhexyl) amino group, and a di (butanoyloxycyclohexyl) amino group;

Di (methylaminomethyl) amino group, di (2-methylaminoethyl) amino group, di (2- (2-methylaminoethoxy) ethyl) amino group, di (4-methylaminobutyl) amino group, di (1-methylamino Propan-2-yl) amino group, di (3-methylaminopropyl) amino group, di (2-methylamino-2-methylpropyl) amino group, di (2-ethylaminoethyl) amino group, di (2- (2-ethyl Aminoethoxy) ethyl) amino group, di (3-ethylaminopropyl) amino group, di (1-ethylaminopropyl) amino group, di (2-isopropylaminoethyl) amino group, di (2- (n-butylamino) ethyl C2-C10 dialkylamino group substituted by dialkylamino groups, such as an amino group, a di (3- (n-hexylamino) propyl) amino group, and a di (4- (cyclohexylamino) butyl) amino group;

Di (methylaminomethoxymethyl) amino group, di (methylaminoethoxyethyl) amino group, di (methylaminoethoxypropyl) amino group, di (ethylaminoethoxypropyl) amino group, di [4- (2'-isobutyl C3-C10 dialkylamino group substituted by the dialkylamino group of alkylamino, such as an amino propoxy) butyl] amino group; %

Di (dimethylaminomethyl) amino group, di (2-dimethylaminoethyl) amino group, di [2- (2-dimethylaminoethoxy) ethyl] amino group, di (4-dimethylaminobutyl) amino group, di (1-dimethylamino Propan-2-yl) amino group, di (3-dimethylaminopropyl) amino group, di (2-dimethylamino-2-methylpropyl) amino group, di (2-diethylaminoethyl) amino group, di [2- (2- Diethylaminoethoxy) ethyl] amino group, di (3-diethylaminopropyl) amino group, di (1-diethylaminopropyl) amino group, di (2-diisopropylaminoethyl) amino group, di [2- (di C3-C15 substituted with dialkylamino groups such as -n-butylamino) ethyl] amino group, di (2-piperidylethyl) amino group and di [3- (di-n-hexylamino) propyl] amino group Alkylamino group;

Di (dimethylaminomethoxymethyl) amino group, di (dimethylaminoethoxyethyl) amino group, di (dimethylaminoethoxypropyl) amino group, di (diethylaminoethoxypropyl) amino group, di (4- (2'-di C4-C15 dialkylamino group substituted by the dialkylamino group of dialkylamino, such as an isobutyl amino propoxy) butyl) amino group;

Di (2-methylthiomethyl) amino group, di (2-methylthioethyl) amino group, di (2-ethylthioethyl) amino group, di (2-n-propylthioethyl) amino group, di (2-isopropylthioethyl A dialkylamino group such as an amino group, a di (2-n-butylthioethyl) amino group, a di (2-isobutylthioethyl) amino group, and a di [(3,5,5-trimethylhexylthio) hexyl] amino group Dialkylamino group having 2 to 15 carbon atoms;

Dialkylamino groups, such as dimethylamino group, diethylamino group, di (n-propyl) amino group, di (iso-propyl) amino group, di (n-butyl) amino group, di (iso-butyl) amino group, di (sec-butyl) amino group, di (t-butyl) amino group, di (n-pentyl) amino group, di (iso-pentyl) amino group, di (neopentyl) amino group, di (2-methylbutyl) amino group, di (n -Hexyl) amino group, di (n-heptyl) amino group, di (n-octyl) amino group, di (2-ethylhexyl) amino group, di (3,5,5-trimethylhexyl) amino group, di (decaryl) amino group, C1-C10, such as a di (methoxyethyl) amino group, a di (ethoxyethyl) amino group, a di (methoxyethoxyethyl) amino group, a di (ethoxyethoxyethyl) amino group, and a di (n-decyl) amino group Dialkylamino group;

C12-20 dialkylalkyl groups, such as a dibenzylamino group, a diphenethylamino group, a bis (4-ethylbenzyl) amino group, and a bis (4-isopropylbenzyl) amino group;

A diarylamino group having 12 to 14 carbon atoms such as a diphenylamino group, a ditolylamino group, a dixylylamino group, an N-phenyl-N-tolylamino group, an N-phenyl-N-xylylamino group, and a dimethylamino group;

C4-C12 dialkenylamino groups, such as a divinylamino group, a diallylamino group, a dibutenylamino group, a diptenenylamino group, a dihexenylamino group, a bis (cyclopentadienyl) amino group, and N-vinyl-N-allylamino group;

Diformylamino group, di (methylcarbonyl) amino group, di (ethylcarbonyl) amino group, di (n-propylcarbonyl) amino group, di (iso-propylcarbonyl) amino group, di (n-butylcarbonyl) amino group , Di (iso-butylcarbonyl) amino group, di (sec-butylcarbonyl) amino group, di (t-butylcarbonyl) amino group, di (n-pentylcarbonyl) amino group, di (iso-pentylcarbonyl) amino group , Di (neopentylcarbonyl) amino group, di (2-methylbutylcarbonyl) amino group, di (benzoyl) amino group, di (methylbenzoyl) amino group, di (ethylbenzoyl) amino group, di (tolylcarbonyl) amino group, di (Propylbenzoyl) amino group, di (4-t-butylbenzoyl) amino group, di (nitrobenzylcarbonyl) amino group, di (3-butoxy-2-naphthoyl) amino group, di (cinnamoyl) amino group, succinic acid nitrogen atom C2-C30 diacylamino groups, such as these;

N-phenyl-N-allylamino group, N- (2-acetyloxyethyl) -N-ethylamino group, N-tolyl-N-methylamino group, N-vinyl-N-methylamino group, N-benzyl-N-allylamino group , N-methyl-ferrocenylamino group, N-ethyl-cobaltosenylamino group, N-butyl- nickellocenylamino group, N-hexyl-octamethyl ferrocenylamino group, N-methyl- octamethyl cobaltosenylamino group, N- C3-C24 di-substituted amino group which has a substituent chosen from substituted or unsubstituted alkyl group, aralkyl group, aryl group, and alkenyl group, such as a methyl-octamethyl nickel selenylamino group, is mentioned.

Specific examples of the methine group which may have a substituent represented by X ¹ to X ⁸ in the azaanulene ring skeleton of the formula (1) are represented by formulas (5) to (12), respectively.

It can be given: wherein, G ¹ ~G ⁸ is a hydrogen atom or represents the meaning of any substituent] a methine group represented by. Examples of preferred substituents include hydrogen atoms; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Cyano group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aralkyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted alkenyl group; Acyloxy group etc. are mentioned.

In addition, in G ¹ to G ⁸ of Formulas 5 to 12, which are substituents of R ¹ to R ¹⁶ and the methine group of the formula ( ¹⁾ , each substituent may be connected via a linking group, and specifically, an aliphatic condensation or an aromatic Formation of the ring by condensation or formation of a heterocycle in which the linking group contains a hetero atom such as a hetero atom or a metal complex residue may be mentioned.

Examples of the linking group when R ¹ to R ¹⁶ and G ^{1 to} G ⁸ bind to each other through an adjacent substituent and a linking group to form a ring include an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a metal atom, a semimetal atom, and the like. Is a group formed by appropriately selecting and combining a hetero atom and a carbon atom, and examples of preferred linking groups are -0-, -S-, -C (= 0)-or a methylene group, methine group and ethynyl which may be substituted; A lene group, a phenylene group, an amino group, an imino group, a metal atom, a semimetal atom, etc. are mentioned, A desired ring can be obtained by combining suitably together. Examples of the ring formed by the linking chain include chain, plane or three-dimensional rings. As a ring obtained as a preferable example of a linking chain when forming a ring by linkage, -CH ₂ -CH ₂ -CH ₂ -CH _2- , -CH ₂ (NO ₂ ) -CH ₂ -CH ₂ -CH _2- , Alicyclic condensed rings with aliphatic chains such as -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -and -CH (Cl) -CH ₂ -CH _2- ;

-CH = CH-CH = CH-, -C (NO ₂ ) = CH-CH = CH-, -C (CH ₃ ) = CH-CH = CH-, -C (CH ₃ ) = CH-CH = CH -, -C (CH ₃ ) = CH-CH = C (CH ₃ )-, -C (OCH ₃ ) = CH-CH = C (OCH ₃ )-, -C (OCH ₂ CH ₂ CH (CH ₃ ) -(OCH ₃ )) = C (Cl) -C (Cl) = C (OCH ₂ CH ₂ CH (CH ₃ )-(OCH ₃ ))-, -C (OCH ₂ CH ₂ CH (CH ₃ ) ₂ ) = C (Cl) -C (Cl) = C (OCH ₂ CH ₂ CH (CH ₃ ) ₂ )-, -CH = C (CH ₃ ) -C (CH ₃ ) = CH-, -C (Cl) = CH-CH = CH-, -C {OCH [CH (CH ₃ ) ₂ ] ₂ } = CH-CH = CH-, -C {OCH [CH (CH ₃ ) ₂ ] ₂ } = C (Br) -CH = CH-, -C {OCH [CH (CH ₃ ) ₂ ] ₂ } = CH-C (Br) = CH-, -C {OCH [CH (CH ₃ ) ₂ ] ₂ } = CH-CH = C ( Br)-, -C (C ₂ H ₅ ) = CH-CH = CH-, -C (C ₂ H ₅ ) = CH-CH = C (C ₂ H ₅ )-, -CH = C (C ₂ H ₅ ) -C (C ₂ H ₅ ) = CH-, -C (Cl) = CH-CH = CH- aromatic condensed ring with aliphatic chain;

-O-CH ₂ -CH ₂ -O-, -O-CH (CH ₃ ) -CH (CH ₃ ) -O-, -COO-CH ₂ -CH _2- , -COO-CH _2- , -CONH- CH ₂ -CH _2- , -CONH-CH _2- , -CON (CH ₃ ) -CH ₂ -CH _2- , -CON (CH ₃ ) -CH _2- , -S-CH ₂ -CH ₂ -S- , An aliphatic chain having a hetero atom in a carbon-carbon atom chain such as -S-CH (CH ₃ ) -CH (CH ₃ ) -S-, -N = CH-CH = N-, -CH = NN = CH- Heterocycles by, or

<Formula>

(M 'represents Fe, Ru, Co, Ni, Os or M "R' ₂ (M" represents Ti, Zr, Hf, Nb, Mo, V, and R 'represents CO, F, Cl, Br, I, the above-described R ¹ ~R ¹⁶ and represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group of 1 to 10 carbon atoms with the same substituent) shows a) a metal complex residue and the like;

Heterocycles; and the like.

General formula (I) of R ¹ ~R ¹⁶ and methine group which is a substituent of a substituted or unsubstituted hydrocarbon group and / or a hydrocarbon group represented by G ¹ ~G ⁸ of formula 5 to formula (12) of the vapor substituted hydroxyl groups, substituted mercapto As an example of the substituted or unsubstituted sulfur atom which has between carbon-carbon atoms in earthenware and a substituted amino group, Unsubstituted sulfur atoms, such as a thia group; Sulfur atoms substituted with oxygen such as sulfonyl group and sulfinyl group; Etc. can be mentioned.

General formula (I) of R ¹ ~R ¹⁶ and methine group which is a substituent of a substituted or unsubstituted hydrocarbon group and / or a hydrocarbon group represented by G ¹ ~G ⁸ of formula 5 to formula (12) of the vapor substituted hydroxyl groups, substituted mercapto As an example of the substituted or unsubstituted nitrogen atom which has between carbon-carbon atoms in earthenware and a substituted amino group, Unsubstituted nitrogen atoms, such as -N =; An imino group in which a hydrogen atom or a hydrocarbon group described above is substituted; Substituted nitrogen atoms, such as these, are mentioned.

Examples of the divalent to tetravalent metal atoms or trivalent tetravalent metal atoms represented by M include metal atoms and semimetal atoms of group IIA to Group A, Group VIII, and Groups IB to VB.

Specific examples of divalent metal atoms that may have a ligand include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Sn, Mg, Pb, Hg, Cd, Ba, Ti, Be, Ca, Heterocyclic compounds such as substituted or unsubstituted 5-membered ring nitrogen-containing aromatic compounds, 6-membered ring nitrogen-containing aromatic compounds, and condensed nitrogen-containing compounds, such as divalent unsubstituted metal atoms or ligands such as Re and Os, are coordinated with carbon monoxide and alcohols And divalent metal atoms.

Examples of the substituted or unsubstituted 5-membered ring nitrogen-containing aromatic compound coordinated with a divalent metal atom include pyrrole, methylpyrrole, dimethylpyrrole, pyrazole, N-methylpyrazole, 3,5-dimethylpyrazole, imidazole, N -Methylimidazole, methylimidazole, 1,2-dimethylimidazole, oxazole, thiazole, 4-methylthiazole, 2,4-dimethylthiazole, 1,2,3-oxadiazole, Triazole, 1,3,4-thiadiazole, 2,5-dimethyl-1,3,4-thiadiazole, and the like.

Examples of the substituted or unsubstituted 6-membered nitrogen-containing aromatic compound coordinated with a divalent metal atom include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethyl Pyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 3,4-dimethylpyridine, 3,5-dimethylpyridine, 2-chloropyridine, 3-chloropyridine, 2-methoxypyridine, pyridazine, 3 -Methylpyridazine, pyrimidine, 4-methylpyrimidine, 2-chloropyrimidine, pyrazine, 2-methylpyrazine, 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2-methoxypyrazine, s-tri Azine and the like.

Examples of the substituted or unsubstituted condensed nitrogen-containing compound coordinated with a divalent metal atom include indole, N-methylindole, 2-methylindole, 3-methylindole, 5-methylindole, 1,2-dimethylindole, 2, 3-dimethylindole, 4-chloroindole, 5-chloroindole, 6-chloroindole, 4-methoxyindole, 5-methoxyindole, 6-methoxyindole, benzimidazole, 2-methylbenzimidazole, 5 -Methylbenzimidazole, 5,6-dimethylbenzimidazole, 5-chlorobenzimidazole, benzothiazole, 2-methylbenzothiazole, 2,5-dimethylbenzothiazole, 2-chlorobenzothiazole, purine , Quinoline, 2-methylquinoline, 3-methylquinoline, 4-methylquinoline, 6-methylquinoline, 7-methylquinoline, 8-methylquinoline, 2,4-dimethylquinoline, 2,6-dimethylquinoline, 2-chloro Quinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, isoquinoline, 1-methylquinoline, quinoxaline, 2-methylquinoxaline, 2,3-dimethylquinoxaline, carbazole, N-methylcarbine Basel, Arc Dean, and the like 9-methyl acridine, phenothiazine.

Preferable specific examples of the divalent metal atom include Cu, Ni, Co, Rh, Zn, Fe, Cu (pyridine) ₂ , Zn (pyridine) ₂ , Co (pyridine) ₂ , Fe (N-methylimidazole), Co And unsubstituted or double-coordinated divalent metal atoms such as (N-methylimidazole).

When n is 0, M of Formula 1 represents a trivalent or tetravalent metal atom or a semimetal atom having a substituent.

As a trivalent metal atom or semimetal atom which has a substituent represented by M, Sc, Ti, V, Cr, Mn, Mo, Ag, U, Fe, Co, Ni, Cu, Y, Nb, Ru, Rh, La , Trivalent, such as Ta, Ir, Au, In, Tl, Bi, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, B, As, Sb An alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryl which may have a halogen atom, a hydroxyl group, or a substituent represented by R ¹ to R ¹⁶ described above as a substituent on an unsubstituted metal atom or an unsubstituted semimetal atom Alkoxy group, aryl group, heteroaryl group, alkoxy group, aryl jade which may have the same halogen atom, hydroxyl group, substituent as oxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio group, amino group Trivalent metal atoms selected by bonding to a period, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, an amino group or a silyloxy group substituted with an alkyl group or an aryl group Is a half-metal atom or a substituent, the same halogen atom as the substituent described above, an alkyl group which may have a substituent, an aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group Heterocyclic compounds such as a substituted or unsubstituted 5-membered ring nitrogen-containing aromatic compound, a 6-membered ring-containing nitrogen-containing aromatic compound, or a condensed nitrogen-containing compound as a ligand to a trivalent metal atom or semimetal atom selected by bonding to a heteroarylthio group or an amino group; And trivalent metal atoms to which carbon monoxide, alcohol and the like are coordinated.

Examples of the silyloxy group substituted with an alkyl group or an aryl group include alkyl such as triarylsilyloxy groups such as trialkylsilyloxy groups such as trimethylsilyloxy group and triethylsilyl group and triphenylsilyloxy group, and dimethylphenylsilyloxy group. An aryl silyloxy group etc. are mentioned.

Preferable specific examples of the trivalent metal atom include Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga-I, In-F, In-Cl, In -Br, In-I, Ti-F, Ti-Cl, Ti-Br, Ti-I, Al-C ₆ H ₅ , Al-C ₆ H ₄ (CH ₃ ), In-C ₆ H ₅ , In- C ₆ H ₄ (CH ₃ ), Mn (OH), Mn (OC ₆ H ₅ ), Mn [OSi (CH ₃ ) ₃ ], Fe-Cl, Fe-Cl (bis (N-methylimidazole)) And mono-substituted trivalent metal atoms such as Fe- (imidazolyloxy) and Ru-Cl.

Preferred specific examples of trivalent semimetal atoms include BF, B-OCH ₃ , BC ₆ H ₅ , BC ₆ H ₄ (CH ₃ ), B (OH), B (OC ₆ H ₅ ), B [OSi (CH ₃₎ ) _3] may be a trivalent metalloid atoms such as 1-substituted.

As a tetravalent metal atom or semimetal atom which has a substituent represented by M, the said technique as a substituent to tetravalent unsubstituted metal atom or unsubstituted semimetal atom, such as Ti, Cr, Sn, Zr, Ge, Mn, Si, A halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, represented by one R ¹ to R ¹⁶ , Heteroarylthio group, the same halogen atom, hydroxyl group, alkyl group which may have a substituent, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, hetero Substituted or unsubstituted five-membered ring-containing nitrogen-containing aromatization as a ligand to a tetravalent metal atom or semimetal atom selected by bonding to an arylthio group, an amino group, or a silyloxy group or an oxygen atom substituted with an alkyl group or an aryl group; Water, it may be mentioned containing aromatic compound, a heterocyclic nitrogen-containing compounds such as chukhwan compound, carbon monoxide, a tetravalent metal atom and which may be coordinated to a nitrogen such as alcohol 6-membered ring.

Preferred specific examples of the tetravalent metal atoms include TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , CrF ₂ , CrCl ₂ , CrBr ₂ , CrI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , SnI ₂ , ZrF ₂ , ZrCl _{2 , ZrBr 2, ZrI 2, GeF} 2, GeCl 2, GeBr 2, GeI 2, MnF 2, MnCl 2, MnBr 2, MnI 2, Ti (OH) 2, Cr (OH) 2, Sn (OH) 2, Zr (OH) ₂ , Ge (OH) ₂ , Mn (OH) ₂ , TiA ₂ , CrA ₂ , SnA ₂ , ZrA ₂ , GeA ₂ , MnA ₂ , Ti (OA) ₂ , Cr (OA) ₂ , Sn (OA ) ₂ , Zr (OA) ₂ , Ge (OA) ₂ , Mn (OA) ₂ , Ti (SA) ₂ , Cr (SA) ₂ , Sn (SA) ₂ , Zr (SA) ₂ , Ge (SA) ₂ , Mn (SA) ₂ , Ti (NHA) ₂ , Cr (NHA) ₂ , Sn (NHA) ₂ , Zr (NHA) ₂ , Ge (NHA) ₂ , Mn (NHA) ₂ , Ti (NA ₂ ) ₂ , Cr (NA ₂ ) ₂ , Sn (NA ₂ ) ₂ , Zr (NA ₂ ) ₂ , Ge (NA ₂ ) ₂ , Mn (NA ₂ ) ₂ [A is an alkyl group represented by R ¹ to R ¹⁶ described above, Disubstituted tetravalent metal atoms, such as an aryl group and a heteroaryl group, or a substituted or unsubstituted alkyl group, aryl group, or heteroaryl group].

Preferable specific examples of the tetravalent semimetal atom include SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , Si (OH) ₂ , SiA ₂ , Si (OA) ₂ , Si (SA) ₂ , Si (NHA) ₂ , Si And di-substituted tetravalent semimetal atoms such as (NA ₂ ) ₂ [A means A as described above].

As a specific example of the oxo metal atom which is a tetravalent metal atom which the oxygen atom couple | bonded, VO, MnO, TiO, etc. are mentioned.

As M, preferably Cu, Ni, Co, Rh, Zn, Fe, MnCl, CoCl, FeCl, Fe (N-methylimidazolyloxy), Fe-Cl (bis (N-methylimidazole)), Cu (pyridine) ₂ , Zn (pyridine) ₂ , Co (pyridine) ₂ , Fe (N-methylimidazole), Co (N-methylimidazole) ₂ , VO, TiO, TiA ₂ , SiA ₂ , SnA ₂ , RuA ₂ , RhA ₂ , GeA ₂ , Si (OA) ₂ , Sn (OA) ₂ , Ge (OA) ₂ , Si (SA) ₂ , Sn (SA) ₂ , Ge (SA) ₂ [A is Means A as described above.].

And when n is 1, M represents a trivalent metal atom and one hydrogen atom or a tetravalent metal atom.

In M, as a trivalent metal atom used with one hydrogen atom, the metal atom of group IIIA-Group A, Group VIII, Group IB-Group B is mentioned. Preferred examples include Sc, Ti, V, Cr, Mn, Mo, Ag, U, Fe, Co, Ni, Cu, Y, Nb, Ru, Rh, La, Ta, Ir, Au, In, Tl, Pb, Bi, Trivalent unsubstituted metal atoms, such as Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, are mentioned. More preferably, Lu, Ce, Sm, Ru, Eu, Y, Rh, etc. are mentioned.

As a tetravalent metal atom represented by M, the metal atom of group IIIA-Group A, group VIII, group IB-Group B is mentioned. Preferred examples include Ti, V, Cr, Mn, Mo, Zr, Nb, Ru, Rh, Ta, Ir, Pb, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Trivalent unsubstituted metal atoms, such as Yb and Lu, are mentioned. More preferably, Zr, Lu, Ce, Ru, Rh, etc. are mentioned.

Moreover, in this invention, the compound further illustrated by General formula (2) can be mentioned as a preferable example as a compound represented by General formula (1).

[Wherein, R ¹⁷ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted Represents an amino group, and each substituent of R ¹⁷ to R ²⁴ may be bonded together via a linking group with each substituent on the tetraazaporphyrin ring to form an aliphatic ring, and substituted in a substituted or unsubstituted hydrocarbon group and / or a hydrocarbon group It may have an oxygen atom, a substituted or unsubstituted sulfur atom, a substituted or unsubstituted nitrogen atom between carbon-carbon atoms in a substituted hydroxyl group, a substituted mercapto group, and a substituted amino group. M ¹ represents a divalent metal atom or substituent which may have a ligand and / or a trivalent or tetravalent metal atom or semimetal atom having a ligand]

In the compound represented by the formula (2) of the present invention, specific examples of R ¹⁷ to R ²⁴ include a hydrogen atom; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Nitro group; Cyano group etc. are mentioned.

Examples of the substituted or unsubstituted hydroxy group of R ¹⁷ to R ²⁴ , the substituted or unsubstituted mercapto group, and the substituted or unsubstituted amino group include the same substituted or unsubstituted hydroxyl group, substituted or unsubstituted as those described above for R ¹ to R ^16. Mercapto group, a substituted or unsubstituted amino group is mentioned.

Examples of the linking group when R ¹⁷ to R ²⁴ are bonded to each other through a linking group to form an aliphatic ring include the same linking groups as those described above for R ¹ to R ¹⁶ .

Examples of the divalent metal atom or substituent which may have a ligand used in M ¹ and / or the trivalent or tetravalent metal atom or semimetal atom having a ligand include the same metal atom as M described above.

In addition, as a compound represented by General formula (1) in this invention, the compound further illustrated by General formula (3) can be mentioned as a preferable example.

[Wherein, R ²⁵ to R ⁴⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted An amino group, X ^{9 to} X ¹⁶ each independently represent a nitrogen atom or a substituted or unsubstituted methine group, and each of the substituents on R ²⁵ to R ⁴⁰ and the methine group may be bonded together via a linking group to form an aliphatic ring, , An oxygen atom, a substituted or unsubstituted sulfur atom, a substituted or unsubstituted nitrogen atom in a substituted or unsubstituted hydrocarbon group and / or a substituted hydroxy group substituted with a hydrocarbon group, a substituted mercapto group, or a carbon-carbon atom in a substituted amino group Can be. In addition, n represents O or 1, when n is 0, M ² represents a trivalent or tetravalent metal atom or semimetal atom having a divalent metal atom or substituent which may have a ligand and / or a ligand, when n is 1, M ² represents a trivalent metal atom and one hydrogen atom or a tetravalent metal atom]

In the compound represented by general formula (3) of the present invention, specific examples of R ²⁶ to R ⁴⁰ include a hydrogen atom; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Nitro group; Cyano group etc. are mentioned.

Examples of the substituted or unsubstituted hydroxy group of R ²⁵ to R ⁴⁰ , the substituted or unsubstituted mercapto group, and the substituted or unsubstituted amino group include the same substituted or unsubstituted hydroxyl group, substituted or unsubstituted as those described above for R ¹ to R ^16. Mercapto group, a substituted or unsubstituted amino group is mentioned.

Examples of the linking group when R ²⁵ to R ⁴⁰ are bonded to each other through a linking group to form an aliphatic ring include the same linking groups as those described above for R ¹ to R ¹⁶ .

As the metal atom or semimetal atom used in M ² , when n is 0, examples of the trivalent or tetravalent metal atom or semimetal atom having a divalent metal atom or substituent which may have a ligand and / or a ligand are as follows. And the same metal atom as M described above. In addition, when n is 1, M ² may be exemplified the same metal atom and a trivalent metal atom and one hydrogen atom or the above-described examples of the tetravalent metal atoms M.

In addition, as a compound represented by General formula (1) in this invention, the compound further illustrated by General formula (4) can be mentioned as a preferable example.

[Wherein, R ⁴¹ to R ⁷² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted mercapto group, a substituted or unsubstituted Represents an amino group, and each substituent of R ⁴¹ to R ⁷² may be bonded together through a substituent and a linking group on each of the phthalocyanine rings, and a substituted hydroxy group and / or a substituted mercapto group substituted in a substituted or unsubstituted hydrocarbon group and / or a hydrocarbon group. It may have an oxygen atom, a substituted or unsubstituted sulfur atom, and a substituted or unsubstituted nitrogen atom between carbon-carbon atoms in the substituted amino group. n represents 0 or 1, when n is 0, M ³ represents a trivalent or tetravalent metal atom or semimetal atom having a divalent metal atom or substituent which may have a ligand 1, and when n is 1 , M ³ represents a trivalent metal atom and one hydrogen atom or a tetravalent metal atom]

In the compound represented by the formula (4) of the present invention, specific examples of R ⁴¹ to R ⁷² include a hydrogen atom; Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Nitro group; Cyano group etc. are mentioned.

Examples of the substituted or unsubstituted hydroxy group of R ⁴¹ to R ⁷² , the substituted or unsubstituted mercapto group, and the substituted or unsubstituted amino group include the same substituted or unsubstituted hydroxyl group, substituted or unsubstituted as those described above for R ¹ to R ^16. Mercapto group, a substituted or unsubstituted amino group is mentioned.

Examples of the linking group when R ⁴¹ to R ⁷² combine with each other through a linking group to form a ring include the same linking groups as those described above for R ¹ to R ¹⁶ .

As the metal atom or semimetal atom used in M ³ , when n is 0, examples of the trivalent or tetravalent metal atom or semimetal atom having a divalent metal atom or substituent which may have a ligand and / or a ligand are as follows. And the same metal atom as M described above. Further, when n is 1, M ³ may be the same metal atom and a trivalent metal atom and one hydrogen atom or the above-described examples of the tetravalent metal atoms M.

Among the azaanulene compounds described in the present invention, the compound of the formula (1) is used in the oscillation wavelength range 350-450 nm of the blue violet nitride semiconductor laser, the red semiconductor laser wavelength 600-650 nm used in the DVD-R, and the CD-R. It is preferably used for recording, reproducing and erasing at a near infrared semiconductor laser wavelength of 750 to 850 nm. Here, the compound of formula 3 is more suitable for recording, reproducing and erasing at a red semiconductor laser wavelength of 600 to 650 nm used in DVD-R, and the compound of formula 4 is a near infrared semiconductor laser wavelength used in CD-R. It is more preferably used for recording, reproducing and erasing at 750 to 850 nm. In particular, the compound of the formula (2) is used for recording, reproducing, and erasing in the wavelength region of both the oscillation wavelength range of 350-450 nm of the blue violet nitride semiconductor laser and the 600-650 nm wavelength of the red semiconductor laser used in the DVD-R. Suitable.

In the compound represented by the formula (1) used in the present invention, n is not limited to 0. For example, for a tetraazaporphyrin (alias: porpyrazine) compound in which X ^{1 to} X ⁴ are all nitrogen, for example, J. Gen . Chem. It is manufactured according to the method described in USSR vo1.47, pp 1954-1958 (l977) and the like. Typically, it can manufacture by the following reaction.

That is, at least one compound represented by the following formulas (13) to (16) is used, and alcohols such as pentanol and hexanol, benzene, toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene, 1,2, Organic metal salts such as acetylacetonate salts, acetate salts and trifluoroacetic acid salts or hydrates thereof, aromatic metal halides, sulfates, nitrates, and perchloric acid in an aromatic solvent such as 4-trichlorobenzene. Inorganic metal salts such as salts, chlorates, hypochlorites or hydrates thereof, or the like, and optionally, by heating in the presence of a base such as 1,8-diazabicyclo [5.4.0] -7-undecene, n It is possible to obtain a phthalocyanine compound or a tetraazaporphyrin compound of the formula (2), wherein ^four of = 0 and X ^{1 to} X 4 are nitrogen.

[Wherein, R ⁷³ to R ⁸⁰ each represent the same meaning as R ¹ to R ⁸ of the formula (1)]

In addition, the tetraazaporphyrin compound of formula (2) is reacted with an acid such as an organic acid such as trifluoroacetic acid in a solvent such as chloroform, or a Grignard reagent such as methylmagnesium bromide is reacted, followed by hydrochloric acid or sulfuric acid. By treatment with an acid such as a metalized tetradazaporphyrin compound can be obtained.

In addition, n = 0, X ¹ ~X for mono-aza porphyrin-based compound is one of the ^four nitrogen is not particularly limited, for example Bul1. Chem. Soc. Jpn., 61, 3539-3547 (l988), Inorg. Chem., 32. 291-296 (l993), Tetrahedron Lett., 36 (10), 1567-1570 (1995), Liebigs Ann. It can be manufactured according to the method described in Chem., 339-359 (l977), Inorganica Chimica Acta, 203.107-114 (1993) and the like. Typically, it can manufacture by the following method, for example.

That is, the dipyromethane compound of the formula (17) and the pyrrole compound of the formula (18) and the formula (9) are reacted in the presence of hydrobromic acid in a solvent such as a halogenated solvent such as methylene chloride or an alcoholic solvent such as ethanol to condensate of the formula 20 or Hydrobromide is obtained.

[In formula, R <^81> , R <^82> , R <^84> , R <^85> , R <^86> , R <^87> , R <^89> and R <^90> represent the same meaning as R <^1> -R <^8> of Formula (1), respectively, and R <^83> , R <^88> , R ⁹¹ has the same meanings as the substituents on the respective X ¹ ~X ⁴ is a methine group of the formula 1, r represents a hydrogen atom or a carboxyl group;

^{[Wherein, R 92, R 93, R} 95, R 96, R 98, R 99, R 101, R 102 represents the same meaning as that of each of R ¹ ~R ⁸ of formula ^{1, R 94, R 97,} R ¹⁰⁰ denotes the same meanings as the substituents on the respective X ¹ ~X ⁴ is a methine group of the formula (1);

Subsequently, the condensate represented by the formula (20) is bromine, iodine, N-bromosuccinimide, N- in a solvent such as an organic acid such as acetic acid, methylene chloride, trifluoroacetic acid, a halogenated solvent or an alcohol solvent such as ethanol. Halogenation with a halogenating agent such as iodine succinimide gives a dihalogenated compound of the formula (21).

[Wherein, R ⁹² to R ¹⁰² each represent the same group as R ⁹² to R ¹⁰² of the general formula (20), and a represents a halogen atom]

Subsequently, in an alcohol solvent such as methanol or ethanol, a halogenated solvent such as methylene chloride or an amide solvent such as N, N-dimethylformamide, inorganic salts such as sulfates, nitrates and halogenated salts of metals or semimetals, or acetic acid Metals or semimetal compounds such as salts and organic metal salts such as acetylacetonate salts, coordinating compounds capable of coordinating to metals such as pyridine, ionic compounds such as anion such as sodium chloride or sodium fluoride, oxidizing agents such as air, N N by the reaction of azide salts such as sodium azide in the presence or absence of a neutralizing agent such as ethyldiisopropylamine or triethanolamine, a phase transfer catalyst such as benzo-18-crown-6-ether, or the like Monoaza porphyrin type compound whose one of = O and X <^1> -X <^4> is nitrogen can be obtained.

Further, the metal complexed monoazaporphyrin compound is reacted with an acid such as an organic acid such as trifluoroacetic acid in a solvent such as chloroform, or a Grignard reagent such as methylmagnesium bromide is reacted. By treating with an acid, a nona metalized monoazaporphyrin compound can be obtained.

In addition, the diazaporphyrin-based compound in which two of n = O and X ^{1 to} X ⁴ are nitrogen is not particularly limited, and examples thereof include J. Chem., Soc. (C), 22-29 (1996), and J. Biochem. , 121, 654-660 (1997), Z. Physiol. Chem. 214, 145 (1933), Die Chemie des Pyrrols, Band II. It is manufactured according to the method described in Halfte 2, pp. 411-414, Akademische Verlagesellschuft, Leipzig (l940) and the like. Representatively, it can be prepared by the following three steps.

First, in the first step, the dipyromethane compounds represented by the formulas (22) and (23) are each bromine, iodine, N-bromosuccinimide, N in a carboxylic acid solvent such as acetic acid or a halogenated hydrocarbon solvent such as methylene chloride. Halogenated with a halogenating agent such as iodosuccinic acid imide to obtain a dipyrromethene compound represented by the formulas (24) and (25), respectively.

[In formula, R <^103> , R <^104> , R <^106> , R <^107> , R <^108> , R <^109> , R <^111> and R <^112> represent the same meaning as R <^1> -R <^8> of general formula (1), and R <^113> , R <^118> is a general formula The same meaning as each substituent on the methine group of 1, r represents a hydrogen atom or a carboxyl group]

[Wherein, R ¹⁰³ ~R ¹¹² represents the same group and each R ¹⁰³ ~R ¹¹² of Formula 22 and Formula 23, a represents a halogen atom;

Subsequently, in the second step, the dipyrromethene compounds of the formulas (24) and (25) are respectively sulphates, nitrates, and halide salts of metals or semimetals in organic solvents such as alcohol solvents such as ethanol and / or amide solvents such as dimethylformamide. Dipyrromethene represented by the formula (26) by using a metal or semimetal compound such as an inorganic salt such as an organic salt or an organic metal salt such as an acetate salt or an acetylacetonate salt and reacting in the presence or absence of an oxidizing agent such as air. Obtain a metal complex.

[Wherein, R ¹¹³ to R ¹²² and a each represent the same group as R ¹¹³ to R ¹¹² and a of Formula 24 and Formula 25, and M ⁴ represents the same meaning as M of Formula 1]

Subsequently, in the third step, the dipyrromethene metal complex 26 is reacted with an azide salt such as sodium azide in an alcohol solvent such as ethanol and / or an organic solvent such as an amide solvent such as dimethylformamide. The diazaporphyrin compound whose two of n = O and X <^1> -X <^4> is nitrogen can be obtained.

Here, the dipyrromethene compounds of the formulas (24) and (25) obtained in the first step are respectively sulfates, nitrates and halogens of metals or semimetals in an organic solvent such as an alcohol solvent such as ethanol and / or an amide solvent such as dimethylformamide. The said diazaporphyrin compound by making it react with the azide salts, such as sodium azide, using inorganic salts, such as a flame, or organic metal salts, such as an acetate and an acetylacetonate salt, etc., in presence or absence of an oxidizing agent, such as air. You can also get

Further, the metal complexed diazaporphyrin compound is reacted with an acid such as an organic acid such as trifluoroacetic acid in a solvent such as chloroform, or a Grignard reagent such as methylmagnesium bromide is reacted with an acid such as hydrochloric acid or sulfuric acid. By treatment with, a metallized diazaazaporphyrin compound can be obtained.

Moreover, it does not specifically limit about the triaza porphyrin type compound in which n = 0 and X <^3> -X <^4> is nitrogen, For example, Can. J. Chem. It is manufactured according to the method described in Vol. 71, 742-753 (1996) and the like. Typically, it can manufacture by the following reaction, for example.

That is, at least one of the unsaturated ketone compounds of the formulas (27) and (28) is heated and reacted with a halogenated metal and / or a metal derivative in the presence or absence of a solvent in the compound represented by Formulas (13) to (16). A triaza porphyrin compound in which three of n = O and X ^{1 to} X ⁴ are nitrogen can be obtained.

[Wherein, R ¹²³ , R ¹²⁴ , R ¹²⁶ , and R ¹²⁷ each have the same meaning as R ¹ to R ⁸ of Formula 1, and R ¹²⁵ and R ¹²⁸ have the same meaning as the substituents on the methine group of Formula 1, respectively. , r represents a hydrogen atom or a carboxyl group]

As another method, at least one compound represented by the above formulas (13) to (16) is used, and the Grignard reagent represented by the following formula (29) is reacted in the presence of a solvent such as ether, and further heated in the presence of an amine such as quinoline. 3 of n = O and X <^1> -X <^4> of General formula (1) are nitrogen, and the triaza porphyrin magnesium complex compound which has a substituted methine group can be obtained.

[Wherein R 'represents the same meaning as a substituent substituted with a methine group of the formula (1), and X' represents a halogen atom]

Further, the metal complexed triazaporphyrin compound is reacted with an acid such as an organic acid such as trifluoroacetic acid in a solvent such as chloroform, or a Grignard reagent such as methylmagnesium bromide is reacted, followed by hydrochloric acid or sulfuric acid. By treatment with an acid, a metalized triaza azaporphyrin compound can be obtained.

In addition, the porphyrin compound in which n = O and X ^{1 to} X ⁴ are all substituted or unsubstituted methine groups, is not particularly limited. For example, J. Org. Chem. It is manufactured according to the method described in Vol. 58 (25), 7245-7257 (1993) and the like. Representatively, it can manufacture by the following reaction.

That is, at least one of the pyrrole compounds represented by the following formulas (30) to (33) and at least one of the aldehyde compounds represented by the following formulas (34) to (37) are used, and the reaction is carried out by heating in a solvent or in the absence of solvent in the presence of propionic acid. Metal-free porphyrin compound whose n = O and X <^1> -X <^{4> of 1} is a substituted or unsubstituted methine group can be obtained.

[Wherein, R ¹²⁹ to R ¹³⁶ have the same meanings as R ¹ to R ⁸ of the formula (1), and R ¹³⁷ to R ¹⁴⁰ have the same meaning as the substituents substituted with a methine group having X ¹ to X ⁴ of the formula (1). ]

Further, as another method, n of the formula 1 is reacted by using a dipyromethanedialdehyde compound represented by the following formula (38) and a dipyromethane compound represented by the following formula (39), in a solvent or in the absence of solvent in the presence of an acid such as propionic acid. It is also possible to obtain a metal-free porphyrin compound in which all of = 0 and X ^{1 to} X ⁴ are substituted or unsubstituted methine groups.

[Wherein, R ¹⁴² , R ¹⁴³ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁸ , R ¹⁴⁹ , R ¹⁵¹ , and R ¹⁵² each have the same meaning as R ¹ to R ⁸ of Formula 1, and R ¹⁴¹ and R ¹⁴⁷ are The same meaning as each substituent on the methine group which is X <^1> -X <^4> of ¹ ]

As for the azaporphyrin-based compound represented by the general formula (1) of the present invention, for n being 1, only the compound represented by the following formulas (40) and 41 or the compound represented by the formula (40) obtained by the above-described manufacturing method or the like is pentanol, hexanol, or the like. Acetylacetonate salt of trivalent or tetravalent metal atom, acetic acid in aromatic solvents such as alcohols, benzene, toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene Organic metal salts or hydrates thereof, such as salts and trifluoroacetate salts, inorganic metal salts or hydrates thereof such as halides, sulfates, nitrates, perchlorates, chlorates, hypochlorites of metal atoms, dimethylamide salts, diethylamide salts, and the like. It can obtain by heating-reacting optionally with di-substituted amide salt etc.

[Wherein, R^One-R¹⁶, X^OneX⁴Is R in Formula 1^One-R¹⁶, X^OneX⁴Wow Each represents the same group]

Or a compound formed by coordinating a compound of the following formula 42 which is a lithium salt instead of the formula 40 or an oxygen-containing hydrocarbon compound such as dimethoxyethane to the compound, and a compound of the following formula 43 which is the lithium salt instead of the formula 41, or The compound can be obtained by reacting the compound in the same manner using a compound obtained by coordinating an oxygen-containing hydrocarbon compound such as dimethoxyethane.

^{[Wherein, R 1 ~R 16, X 1} ~X 8 represents the same groups respectively and ^{R 1 ~R 16, X 1 ~X} 8 of formula (1);

In addition, the compound of the formula (44) wherein the central metal as the compound of the present invention is a trivalent metal and a hydrogen atom is selected from a halogenated solvent such as dichloromethane, chloroform, dichloroethane, trichloroethane, and the like. By reacting the oxidizing agent and optionally by heating, a compound of formula 45 can be obtained wherein the central metal as the compound of the present invention is a tetravalent metal.

[Wherein, R ¹⁵³ to R ¹⁸⁴ represent the same group as R ¹ to R ¹⁶ in the formula (2), M ⁵ represents a trivalent metal atom, M ⁸ represents a tetravalent metal atom, and X ^{9 to} X ²⁴ are and X ¹ ~X ⁸ of formula (1) represents the same meanings, respectively;

And the compound of the following general formula (46) uses silver compounds, such as silver trifluoroacetic acid, as a reaction support agent, and uses benzene, toluene, xylene, 1-chloronaphthalene, 1,2-dichlorobenzene, 1,2,4-trichloro In some aromatic solvents such as robenzene, the compound of formula 47, which is a compound of the present invention, may be obtained by optionally heating with the lithium compound of formula 42 or 48.

[Wherein, R ¹⁸⁵ to R ¹⁰⁸ represent the same group as R ¹ to R ¹⁶ of the formula (1), M ⁷ and M ⁸ each represent a tetravalent metal atom, and Q ¹ and Q ² represent a fluorine atom, a chlorine atom and bromine A halogen atom such as an atom, an iodine atom, etc., and X ^{9 to} X ²⁴ each represent the same meaning as X ¹ to X ⁸ of the general formula [1];

In addition, R ¹ ~R by the synthesis method of Political Science and Law, such as on what is a hydrogen atom any substituent of ^16, such as nitration, halogenation, formylation, amination, carboxylation, hydroxylation, acylation, elimination reaction The compound of the formula (1) in which the selected hydrogen atom is substituted with an arbitrary substituent and in which hydrogen atom is substituted may be further obtained by using a synthesis method such as reduction, oxidation, isomerization, and transition, if necessary.

In addition, although notation of a substituent etc. is shown according to General formula (1), about Formula (2)-Formula 4, it is contained in General formula (1), The substitution of a corresponding substituent etc. is obvious. The pigment | dye of the recording layer which comprises the optical recording medium of this invention consists of a 1 type or more aza- alenurene compound, especially the compound of the formula (1)-(4) further, If necessary, wavelength 290nm-690 as needed. It has an absorption maximum in nm, and can also mix with the pigment compound of that excepting the above with big refractive index in 300 nm-900 nm. Specifically, a cyanine compound, a squarylium compound, a naphthoquinone compound, an anthraquinone compound, a tetrapyraporpyrazine compound, an indophenol compound, a pyryllium compound, a thiopyryllium compound, an azulenium compound, a tri Phenylmethane compounds, xanthene compounds, inda-srene compounds, indigo compounds, thioindigo compounds, merocyanine compounds, thiazine compounds, acridine compounds, oxazine compounds, dipyrromethene compounds, oxazole compounds Etc., and a mixture of a plurality of compounds may be used. The mixing ratio of these compounds is about 0.1 mass%-about 30 mass%.

When forming the recording layer, if necessary, the compounds represented by the formula (1) are recorded, regenerated and erased with compounds such as quenchers, compound pyrolysis accelerators, ultraviolet absorbers, adhesives, endothermic or endothermic decomposable compounds, or solubility enhancers. It may also be introduced as a substituent to the compound represented by the formula (1) so that the molecular weight is less than 3000, effectively or undamaged to the operation.

As a specific example of a quencher, metal complexes, such as an acetylacetonate type, a bisdithiol type, such as a bisdithio- (alpha)-diketone type, a bisphenyldithiol type, a thiocateconal type, a salicylic aldehyde oxime type, and a thiobisphenolate type, are preferable. Do. Also suitable are amines. The compound pyrolysis accelerator is not particularly limited as long as it can confirm the promotion of thermal decomposition of the compound by thermal loss analysis (TG analysis) or the like, and examples thereof include metal compounds such as metal-based anti-knocking agents, metallocene compounds, and acetylacetonate-based metal complexes. Can be mentioned. Metal-based examples of the anti-knock fourth ethyl lead and other lead-based compounds, Symantec Transistor _{[Mn (C 5 H 5)} (CO) 3] Mn -based compounds such as further examples of the metallocene compounds of iron bis-cyclopentadienyl complexes In addition to (ferrocene), there are biscyclopentadienyl complexes such as Ti, V, Mn, Cr, Co, Ni, Mo, Ru, Rh, Zr, Lu, Ta, W, Os, Ir, Sc, and Y. Among them, ferrocene, ruthenocene, osmocene, nickellocene, titanocene and derivatives thereof have a good thermal decomposition promoting effect.

Other iron-based metal compounds include organic iron oxide compounds such as iron formate, iron oxalate, iron lauryl acid, iron naphthenate, iron stearate, and iron acetate in addition to metallocene, acetylacetonato iron complex, phenanthroin iron complex, bispyridine iron Chelate iron complexes, carbonyl iron complexes such as ethylenediamine iron complex, ethylenediamine iron acetate complex, diethylenetriamine iron complex, diethylene glycol dimethyl ether iron complex, diphosphino iron complex, dimethylglyoxymato iron complex, Iron complexes such as cyano iron complexes and ammine iron complexes, iron halides such as ferrous chloride, ferric chloride, ferrous bromide and ferric bromide, or inorganic iron salts such as iron nitrate and iron sulfate, and further iron oxides Can be mentioned. It is preferable that the thermal decomposition accelerator used here is soluble in an organic solvent and has good heat and moisture resistance and light resistance.

As an endothermic or endothermic decomposable compound, the compound of Unexamined-Japanese-Patent No. 10-291366, or the compound which has a substituent described in the publication are mentioned. The various quenchers, compound pyrolysis accelerators, and endothermic or endothermic decomposable compounds described above may be used in one kind or in combination of two or more kinds, if necessary.

Alternatively, it is also possible to introduce a compound having a quencher ability, a compound pyrolysis promoting ability, an ultraviolet absorbing ability, and an adhesion ability as a substituent of the azaanulene compound described in the present invention, especially the compound represented by the formula (1).

That is, with respect to the azaanulene compound residue of the formula (1) described in the present invention, a compound residue having a quencher ability, compound thermal decomposition promoting ability, ultraviolet absorbing ability, adhesion ability, endothermic ability or endothermic resolution ability is at least one single bond, double bond It is also possible to form one molecule by chemically bonding by triple bonding. Preferably, each substituent of the azaanulene ring of Formula 1 is

-(L ⁿ )-(J ⁿ )

[Wherein L ⁿ is at least one selected from a bond to an azaanulene compound of formula (1), that is, a methylene group, a methine group, an amino group, an imino group, an oxygen atom or a sulfur atom which may be a single bond or a substituted Represents an atomic chain having 1 to 20 atoms linked to each other, and J ⁿ represents a compound residue corresponding to R ¹ to R ¹⁶ having a quencher, a compound pyrolysis accelerator, an ultraviolet absorber, adhesion, an endothermic ability, or an endothermic decomposition ability. Formula 49 wherein the substituents represented or each substituent of the azaanulene ring of Formula 1 is bonded to a separate substituent to each other

-(L ^m1 )-(J ^m )-(L ^m2 )-

[Wherein, ^{m m1} and L ^m2 are adjacent to each other and are also bonded to the azaporphyrin compound of formula (2), that is, a methylene group, a methine group, an amino group, an imino group, an oxygen atom, or sulfur which may be a single bond or substituted Represents an atomic chain of atomic moieties 1 to 20 selected by at least one member of the atom, and J ^m corresponds to R ¹ to R ²² having a quencher, a compound pyrolysis accelerator, an ultraviolet absorber, adhesion ability, endothermic ability, or endothermic resolution; The compound residue shown to] is mentioned.

Examples of preferred atomic chains of L ⁿ , L ^m1 and L ^m2 include a single bond, a methylene group, an imino group, a thia group, -C (= O) -OCH _2- , -C (= O) -OCH (CH ₃ ) -, -OCH _2- , -OCH (CH ₃ )-, -CH ₂ OCH _2- , -CH ₂ OCH (CH ₃ )-, -CH (CH ₃ ) OCH (CH ₃ )-, -OC (= O )-, -CH = CH-, -CH = N-, -C (= O)-, -CH = CH-C (= O) O-, -C (C = O) CH ₂ CH ₂ C (= O) -O-, the group in which these groups were substituted by the substituent mentioned above, etc. are mentioned.

Preferred examples of J ⁿ , J ^m include metallocene residues such as ferrocene residues, cobaltocene residues, nickellocene residues, ruthenocene residues, osmocene residues, titanocene residues and the like.

Suitable skeleton examples of the formula (48) include the following metal complex residues.

<Formula>

(M 'represents Fe, Ru, Co, Ni, Os or M "Z' ₂ (M" represents Ti, Zr, Hf, Nb, Mo, V, Z 'represents CO, F, Cl, Br, I, It represents the above-described R ¹ ~R ¹⁶ and represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group of 1 to 10 carbon atoms with the same substituent))

Moreover, the following metal complex residue is mentioned as a suitable skeleton example of general formula (49).

<Formula>

(M 'represents Fe, Ru, Co, Ni, Os or M "Z' ₂ (M" represents Ti, Zr, Hf, Nb, Mo, V, Z 'represents CO, F, Cl, Br, I, It represents the above-described R ¹ ~R ¹⁶ and represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group of 1 to 10 carbon atoms with the same substituent))

In the compound group, for example, the refractive index n≥1.9 in the wavelength λ = 400 nm vicinity can be realized. Particularly, in the phthalocyanine-based, azaporphyrin-based and porphyrin-based pigments, a clear band having a Soret Band in the ultraviolet region of 400 nm or less, which is typically represented by a Q band or the like on the long wavelength side within 400 nm of the Sore Band There is an absorption band with maximum values. The absorption coefficient k and the refractive index n in the gentle portion of the sore band are adjusted to satisfy the above conditions at the recording wavelength?.

Thus, various substituent modifications may be made to the mother nucleus of the basic molecule of the organic dye selected, thereby optimizing the light absorption spectrum and improving workability such as solubility of the dye. These materials can form a film | membrane by melt | dissolving or disperse | distributing in a suitable solvent normally and apply | coating and drying by a spin coat method, a spray method, etc. In addition, for recording between the grooves (land portions) and the inside grooves (groove portions) of the guide grooves formed in the substrate or the light transmitting layer for higher density recording (land groove recording), the pigments in both grooves and lands are used. In order to achieve uniform control of the film thickness, a vacuum deposition method or the like is applied. The recording layer film thickness is preferably formed in the range of 20 to 200 nm. More preferably, it is 20-120 nm. In order to suppress thermal interference and to achieve high recording density, it is preferable to secure a high refractive index of the organic dye recording film and to make the film thickness thin.

In the optical recording medium of the present invention, a reflective layer can be formed adjacent to the recording layer as shown in Figs. 1 and 2 described above. As a material of a reflection layer, metals, such as gold, silver, aluminum, platinum, copper, and the alloy containing these are mentioned. On the other hand, in the case of using a blue-violet laser having a wavelength of 390 to 430 nm, silver, aluminum, and an alloy containing them are preferable in terms of cost and optical characteristics, and alloys such as silver, Ti, Pd, and Cu, which are particularly durable, The system is preferred. The film thickness of a reflection layer is 20-120 nm normally, Preferably it is 10-80 nm. Instead of the metal reflective film, it may be composed of alternating laminated films of dielectric reflective films (low refractive index dielectric films / high refractive index dielectric films). For example, when setting a relatively low reflectance of a disk, a simple configuration such as a two-layer laminated film of a quarter wavelength film of SiO ₂ (n = 1.46) and a quarter wavelength film of Si ₃ N ₄ (n = 2.0) Can be used. The film structure of the disk which does not use the metal thin film layer at all may be adopted. As the method for forming the reflective layer, a vacuum vapor deposition method, a sputtering method, an ion beam sputtering method, or the like can be used.

In the structure of FIG. 1, the protective film 4 is formed by spin-coating organic materials, such as an ultraviolet curable resin and a thermosetting resin, on the reflective layer 3, for example. In addition, as shown in FIG. 1, a dummy substrate may be attached onto the protective film as in the conventional DVD.

Also in the case of the structure as shown in FIG. 3, the reflective layer 2 and the recording layer 3 are sequentially formed on the substrate 1 on which the guide grooves and the like are formed, and the ultraviolet curable resin is formed on the recording layer 3. After coating, the light was irradiated and cured to form a light transmitting layer 8. In addition, the light transmitting layer 8 may be separately formed into a film with a uniform thickness, and may be attached via an adhesive layer such as an ultraviolet curable resin or a pressure sensitive adhesive.

By forming a transparent protective layer between the substrate and the recording layer, it is also effective to suppress deformation of the substrate due to heat generated during recording. In addition, in the case where the light transmitting layer 8 is formed on the recording layer 3 through the adhesive as shown in FIG. 3, in order to suppress the deformation of the substrate and to prevent the organic pigment from melting in the ultraviolet curable resin, It is also effective to form the transparent protective layer 4 between these layers. The transparent protective layer 4 is made of metal (eg Mg, Al, Ti, Zn, Ga, Zr, In, Sn, Sb, Ba, Hf, Ta, Sc, Y, rare earth elements) or semimetals (Si, Ge) It can be formed from a material consisting of a single substance such as oxides, nitrides, sulfides, and fluorides, and mixtures thereof. A vacuum vapor deposition method, a sputtering method, an ion beam sputtering method, etc. can also be used for the formation method of these transparent protective films. In addition, in the optical recording medium having this configuration, a sheet made of polycarbonate, for example, formed with a guide groove formed by a stamper thermal transfer having a thickness of 10 to 177 mu m by injection molding or cast method, is used as the light transmitting layer. The recording layer and the reflective layer which consist of organic dye on it are formed into a film in this order, and the board | substrate can be further attached.

In addition, by forming the transparent protective layer adjacent to both sides of the recording layer, it is possible to suppress the deformation of the substrate, the reflective layer, the protective film or the light transmitting layer due to the heat generated during the recording more completely, thereby improving the repeated rewriting characteristics.

In order to ensure initial reflectance and signal modulation degree in accordance with the standards of CD, DVD, DVR, etc., the film thickness of the recording film, the reflection film, and the transparent protective film is a recording film or a reflection film having an appropriate optical constant in the recording laser wavelength. By using the transparent protective film material and calculating the reflectance of the multilayer thin film structure in consideration of the effect of light multiple reflection, each can be optimized.

Since the optical recording medium according to the present invention has a form in which one or more kinds of thin films are laminated as described above, it is possible to take advantage of the fact that multiple interferences of light occur, and to specify the initial reflectance according to each standard. It is important to set the film thickness of each layer so that it is within a range and that the modulation degree of the detected information signal is maximum. Therefore, the method of calculating the reflectance: the effective Fresnel counting method is described in particular for the effect of multiple interferences of this light.

When r ₁ and r ₂ are Fresnel coefficients in the medium (n ₀ ), medium (n ₁ ), medium (n ₁ ) and medium (n ₂ ) of FIG. 4, the amplitude reflectance of the monolayer film is the incident angle of the laser beam. If is θ,

Given by here

The phase difference between adjacent reflected waves and transmitted waves is 2δ ₁ . According to Stokes' theorem, the light travels from the Fresnel coefficients in the forward direction and the Fresnel coefficients in the reverse direction (shown with dashes).

The relationship is established. therefore,

Is displayed.

In order to obtain the reflectance of the multilayer film, using a Fresnel coefficient before and after the two boundaries of the final layer (L), and considered as one virtual boundary by calculating the multiple interference as described above, and the R _L at this time The sequential calculation is performed toward the upper layer with the effective Fresnel coefficient. In other words,

In the final layer, the complex reflectance is calculated by the above calculation method using the final layer as a single layer film.

Becomes Hereinafter, similarly about j layer

Since it can be expressed as, the reflectance in the multilayer film can be calculated by sequentially calculating the final layer to the first layer.

For example, the polycarbonate substrate 1 shown in FIG. 3, the silver reflecting film 2 having a film thickness of 15 nm, and the organic dye recording film 3 (n, k) = (1.95, 0.15) (the film thickness is a variable parameter). Fig. 5 shows an example of calculation of reflectance when recording and reproducing an optical recording medium having a film thickness of 30 nm SiO ₂ protective film 4 and a polycarbonate light transmitting layer 8 sequentially from the light transmitting layer side. Indicates. For example, when the film thickness of the organic dye recording film 3 is 80 nm, when the initial reflectance before recording is 15% and the refractive index n of the organic pigment film after the base is n = 1.7, the reflectance becomes 8%, and the modulation degree = (Initial reflectance-reflectance after recording) / The organic pigment film thickness of the low reflectivity type medium structure suitable for performing high-to-low recording of the initial reflectance = 47% is determined. In the case of the high reflectivity type, the film thickness of the silver reflecting film is made thicker, and the film structure is different even when low-to-high recording is performed, but optimization is possible by the same calculation method.

Although the present invention has been described as a rewritable type, the recording / reproducing method and the form of the recording medium do not differ from the conventional write-once optical recording medium at all unless the erasing operation is performed. Therefore, the write once optical recording medium is recorded only once. It is also valid as. Therefore, it is possible to ensure high compatibility with the prior art. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited only to these Examples.

Example 1

This example is an example of a DVD using a blue laser having a wavelength λ = 405 nm.

The polycarbonate board | substrate was produced by the injection molding method from the stamper disk which has a groove shape of pitch 0.6 micrometer, groove depth 50 nm, and groove width 0.28 micrometer by thickness 0.6mm and outer diameter 120mm. The film structure in this example is as shown in FIG. Tetraaza porphyrin pigment "tetra-t-butyl-5,10,15,20-tetraaza porphyrin oxovanadium (IV)" represented by the general formula (A) as a recording layer 2 on this substrate was subjected to vacuum deposition. The film was formed on the groove such that the film thickness was 60 nm. The refractive index and absorption coefficient of this recording layer 2 were n = 1.8 and R = 0.05 at 405 nm. Subsequently, a silver reflective layer 3 having a thickness of 100 nm was formed on the recording layer by the sputtering method, and then UV curable resin “SD17” (manufactured by Dainippon Ink) was applied on the reflective layer 3 by a spin coating method. A film was formed to a thickness of 3 mu m to form a protective film 4, and a UV adhesive was applied thereon to attach a dummy substrate (made of polycarbonate) having a thickness of 0.6 mm to produce an optical recording medium having the same appearance as a DVD. At this time, the initial reflectance of the disk was 23%.

A simple repetitive signal in which the recording medium corresponded to the pit length = 0.5 µm in the groove through a polycarbonate substrate by an optical disk evaluation device equipped with a pulse-tech high school manufactured blue pulse laser was wavelength 405 nm, NA = 0.65, and line speed = 3.5 m / s and recording power = 8.5 kW. As a result of reproducing the recording unit with reproduction power = 0.5 Hz, C / N = 59 Hz was obtained. 6 is an RF signal output of this recording pattern.

After recording, the track was erased with continuous (DC) light having an erase power of 3.7 kV. As a result, the remaining signal amount was C / N = 43 kV, and the erasing ratio was 15 kV. Fig. 7 shows the RF signal output at this time. Something left over is visible. Further, rewriting was performed on the same track under the same conditions as the above recording, whereby C / N = 56 ms was obtained. 8 shows the RF signal output at this time. This recording and erasing was repeated 20 times on the same track, whereby a rewrite characteristic evaluation was performed to obtain almost the same C / N values.

Example 2

This example is also an example of a DVD using a blue laser having a wavelength of λ = 405 nm.

The same substrate, organic dye recording film, silver reflecting film, and protective film as in Example 1 were used. The film structure in this example is shown in FIG. The difference from the first embodiment is that the SiO ₂ having a thickness of 30 nm is formed by the sputtering method between the substrate 1 and the recording film 3 and between the recording film 3 and the reflective film 5, respectively. It is a point formed into a film as the transparent protective layer 6. The initial reflectance of the disk was 12%, which is almost in agreement with the calculated value.

A simple repetitive signal corresponding to a pit length = 0.5 mu m was recorded under the same conditions as in Example 1.

As a result of reproducing the recording section with a reproduction power of 0.5 Hz, a C / N ratio of 52 Hz was confirmed. 9 is the RF signal output for this recording pattern.

After recording, the track was erased with continuous (DC) light having an erase power of 3.7 kW. As a result, the remaining signal amount was C / N = 19 kW and an erase ratio of 32 kW was obtained. Fig. 10 shows that the RF signal output at this time is almost completely erased. Further, rewriting was performed on the same track under the same conditions as the above recording, whereby C / N = 51 ms was obtained. 11 is the RF signal output for this recording pattern. This recording and erasing was repeated 20 times on the same track. As a result of rewriting characteristic evaluation, signal degradation hardly occurred and the C / N secured 51 Hz. As can be seen in FIG. 12, signal degradation is hardly observed. By sandwiching both sides of the recording film with a hard dielectric (SiO _{2 in} this example), it is believed that the deformation occurs only in the organic dye recording film, resulting in improved repetitive rewriting performance by suppressing the influence on the substrate or the reflective film. . 21A, 21B, and 21C show strain traces on the dye layer side when SEM observation of the peeling interface between the substrate-side SiO ₂ dielectric layer and the dye layer after erasing, after erasing, and after rewriting. In addition, it is shown in Figure 21D SiO ₂ dielectric layer side interface of the SEM observation image after the recording. It is noteworthy that almost no deformation traces remain on the surface of the SiO ₂ dielectric layer adjacent to the dye layer, and the dome-shaped void traces are visible only corresponding to the recording portion in the dye layer. Moreover, it was observed directly that this dome-shaped deformation | transformation trace was smoothed by the erase operation by a laser. On the other hand, the surface of the substrate-side SiO ₂ dielectric layer did not change even after erasing and rewriting.

Example 3

This example is an example of a DVR (optical disk for recording and reproducing through a light transmitting layer having a thickness of 10 to 177 mu m) using a blue laser having a wavelength of? = 405 nm.

An example of the film configuration of FIG. 3 is shown for a recording medium capable of satisfactorily recording and reproducing in an optical system having a wavelength of 405 nm and NA = 0.85. Here, the polycarbonate substrate 1 is formed with guide grooves having a pitch of track pitch of 0.64 占 퐉, and the width thereof is set to almost 50% so as to be recorded in both land grooves. That is, the actual track pitch is 0.32 mu m. In addition, the depth of the groove is 40 nm. A reflective film 2 of a silver alloy having a film thickness of 12 nm is formed thereon by a sputtering method, and as the organic dye film 3, a diazaporphyrin dye represented by the following general formula (B) "2,8,12,18" -Tetraethyl-3,7,13,17-tetramethyl-5,15-diazaporpyringuri (II) ", and the like.

The film thickness of the organic dye film 3 was 75 nm, and its optical constants were refractive index n = 1.9 and k = 0.15. As the transparent protective layer 7, SiO ₂ having a film thickness of 30 nm was formed by the sputtering method. The purpose of this film is to increase the hardness of the surface and to improve the repeat recording characteristics, but it can be used for protecting the recording film here. . The light transmitting layer has a thickness of 100 μm as described above. This layer took the method of sticking a polycarbonate sheet using a pressure-sensitive adhesive (PSA), and set it so that the thickness which combined these was set to 100 micrometers.

The initial reflectance of the optical disk thus produced was 14%, which is close to the calculated design value. The recording was performed at a line speed of 5.72 m / s, the reproduction optical power at 0.3 kW, and the recording pattern at a single carrier wave length of 0.35 m. In addition, in the recording of a single mark, seven equal-width pulse trains were incident at a pulse / space ratio of 50%, the peak power was 6.0 Hz, and the C / N was measured by the spectrum analyzer at an RBW of 30 Hz. Was evaluated.

In the case of the optical recording medium, a value of 45 Hz was obtained as a result of the above recording and reproducing experiment. Fig. 13 is the RF signal output for this recording pattern.

After recording, the track was erased twice with continuous (DC) light having an erase power of 3.0 kV. As a result, the amount of signal left after erasing was C / N = 10 kV and an erasing ratio of 32 kV was obtained. Fig. 14 shows the RF signal output at this time. In addition, rewriting was performed on the same track under the same conditions as the above recording, and as a result, a C / N value of 43 ms was obtained. Fig. 15 shows the RF signal output at this time. This recording and erasing was repeated 10 times on the same track to evaluate the rewriting characteristics. However, 43 C / N was always secured.

The C / N value of single-carrier recording with a recording mark length of 0.173 μm of the disk was 42 dB, and the C / N value of single carrier recording with a recording mark length of 0.173 μm was 51 dB. As a result of performing random pattern recording of (1, 7) code of 0.38 占 퐉, a pattern as shown in FIG. 16 was obtained.

Example 4

This example is also an example of a DVR (optical disk for recording and reproducing through a light transmitting layer having a thickness of 10 to 177 mu m) using a blue laser having a wavelength of? = 405 nm.

The same polycarbonate substrate as in Example 3 was used. The film structure in this example is as shown in FIG.

Polycarbonate substrate 1 / dielectric film 1 (9) / dielectric film 2 (10) / organic dye recording film 3 / transparent protective layer 7 / light transmitting layer 8.

On the substrate 1, Si ₃ N ₄ (n = 2.0) having a thickness of 60 nm and SiO ₂ (n = 1.46) having a thickness of 60 nm are mixed with nitrogen gas and oxygen gas with an argon sputtering operation gas, respectively. It laminated | stacked sequentially by the reactive sputtering method which used the silicon target for the target. These films have a function of protecting the organic dye recording layer and preventing deformation of the recording mark from affecting the substrate side, and also include a recording layer and a transparent protective layer described later, and the initial reflectance of the disk conforms to the standard (DVR- In the case of Blue, the film thickness is determined to be 15% to 25%).

Then, the monoaza porphyrin pigment represented by the above formula (C) "2,3,7,8,13,17-hexaethyl-12,18-dimethyl-5-aza porphyrin copper (II)" is vacuumed as a recording layer. The film was formed so as to have a film thickness of 50 nm by the vapor deposition method. The refractive index and absorption coefficient of this recording layer were n = 2.1 and k = 0.1 at 400 nm. Subsequently, a 30 nm-thick SiO ₂ transparent protective layer was formed on the recording layer by sputtering. The following is the same as in Example 3.

The optical disk thus produced did not use a metal reflecting film, and caused multiple reflections, which resulted in a value consistent with the designed value calculated by the calculation that the reflectance at a light source of 405 nm is about 20%.

The recording was performed at a line speed of 5.72 m / s, the reproduction light power was 0.3 kW, and the recording pattern was a single carrier having a mark length of 0.35 m. In addition, in the recording of a single mark, seven equal-width pulse trains were incident at a pulse / space ratio of 50%, the peak power was 5.0 mW, and the C / N was measured at a RBW of 30 mW by a spectrum analyzer. The characteristics of the were evaluated. In the case of the optical recording medium described above, a value of 48 kHz was obtained as a result of the above recording / reproducing experiment. After recording, the track was erased with continuous (DC) light having an erasing power of 3.0 kV. As a result, the amount of signal left after erasing was C / N = 25 mV, and the erasing ratio was 23 mV. Further, on the same track, rewriting was performed under the same conditions as the above recording, and as a result, a C / N value of 48 ms was obtained. This recording and erasing was repeated 10 times on the same track, but the C / N value of 1 dB or less was slightly changed until the first three times, but finally, 48 C / N was secured.

Example 5

This example is an example of DVD using a red laser of wavelength lambda = 658 nm.

The recording medium obtained in Example 1 was used. However, the recording film was formed on the substrate by using a tetraazaporphyrin dye with an ethylcyclohexane solution (20 g / l) so as to have a film thickness of 90 nm on the groove by spin coating. Guide grooves of the substrate have a track pitch of 0.74 µm, a width of 0.33 µm, and a groove depth of 150 nm. The refractive index and absorption coefficient of the recording layer were n = 2.1, k = 0.05. Subsequently, a 30 nm thick SiO ₂ transparent protective layer was formed on the recording layer by the sputtering method, and a 100 nm thick silver reflective layer was formed on the recording layer by the sputtering method. SD17 ”(manufactured by Dainippon Ink, Inc.) was formed into a protective film by spin coating to form a protective film. A UV adhesive was applied thereon to attach a dummy substrate (made of polycarbonate) having a thickness of 0.6 mm to An optical recording medium of the same appearance was produced. At this time, the initial reflectance of the disk was 47%. A simple repetitive signal corresponding to a pit length = 0.8 μm in a groove was recorded at a wavelength of 658 nm, NA = 0.60, and line speed = 3.5 m / s by an optical disc evaluation device equipped with a red laser laser manufactured by Pulse Tech High School. The power was recorded under the condition of 9 kW. As a result of reproducing the recording section with reproducing power = 0.5 mW, C / N = 58 mW was obtained.

After recording, the track was erased with continuous (DC) light having an erase power of 4 kV. As a result, the amount of the signal left after erasing was C / N = 30 kV and an erase ratio of 28 kV was obtained. Further, rewriting was performed on the same track under the same conditions as the above recording, whereby C / N = 55 ms was obtained. This recording and erasing was repeated 20 times on the same track to evaluate rewriting characteristics, but the signal deterioration was hardly seen.

Example 6

This example is also an example of a CD using an infrared laser having a wavelength of λ = 780 nm.

A 30 nm thick SiO ₂ transparent protective layer was formed by sputtering on a substrate having a track pitch of 0.74 µm, a width of 0.33 µm, and a groove depth of 170 nm by sputtering. Then, a phthalocyanine dye was added to an ethylcyclohexane solution (20 g / 1) was used to form a film on the groove by spin coating so as to have a thickness of 100 nm. The refractive index and absorption coefficient of the recording layer were n = 2.2, k = 0.1. In addition, a 100 nm thick silver reflective layer was formed by a sputtering method, and then a UV curable resin "SD17" (manufactured by Dainippon Ink) was formed into a protective film by a spin coating method on the reflective layer. It was. At this time, the initial reflectance of the disk was 68%. A simple repetitive signal corresponding to a pit length = 1.2 μm in a groove through a polycarbonate substrate by a near-red laser-mounted optical disk evaluation device manufactured by Pulse Tech High School Co., Ltd., has a wavelength of 781 nm, NA = 0.50, and line speed = 2.4 m / s, The recording power was recorded under the condition of 10.5 kW. As a result of reproducing the recording section with reproduction power = 0.7 kW, C / N = 57 kW was obtained. 18 shows RF signal output at this time.

After recording, the track was erased with continuous (DC) light having an erase power of 3 kHz. As a result, the amount of signal remaining after erasing was C / N = 33 kHz, and an erase ratio of 24 ㏈ was obtained. Fig. 19 shows the RF signal output at this time. In addition, rewriting was performed on the same track under the same conditions as the above recording, whereby C / N = 54 ms was obtained. 20 shows the RF signal output at this time. This recording and erasing was repeated 20 times on the same track to evaluate rewriting characteristics, but the signal deterioration was hardly seen.

As can be seen from the above description, according to the present invention, the laser beam of the same wavelength can be used in the recording, reproducing and erasing operation, and the simple recording and reproducing equipped with one laser light source, in particular a small and lightweight laser diode The apparatus can provide a rewritable optical information recording medium. In particular, a conventional CD-RW drive or DVD-RW drive can be used as it is as a recording / reproducing apparatus of the optical recording medium of the present invention. Furthermore, simply adding an erase function to a CD-R drive or DVD-R drive can be just as useful. No complicated signal detection such as polarized optics is required. In addition, since recording, reproducing and erasing operations at different laser wavelengths are possible, the present invention can be applied to a hybrid drive of CD and DVD.

In the optical recording medium of the present invention, since the recording layer is made of a thin organic dye film itself having a uniform film formation and is changed by laser irradiation, the noise level is sufficiently low, and a high light modulation degree (contrast), i.e., high C / It has N value. The azaapulin compounds used in the optical recording medium of the present invention, particularly azaporphyrins such as phthalocyanine series, naphthalocyanine series, mono to tetraazaporphyrin series, porphyrins and metal complexes thereof, absorb light according to the laser wavelength used. Since the spectrum can be adjusted, an optical recording medium suitable for a recording / reproducing apparatus using semiconductor lasers of various wavelengths can be provided. In particular, in order to achieve high recording density, an optical recording medium adapted to short wavelength lasers such as ultraviolet and blue violet lasers is possible.

In addition, by using optical multiple reflections in combination with a dielectric protective film or a reflective film, the reflectance can be easily set before and after recording, and the recording method can be freely selected. Both land groove recording and in groove recording can be performed by using a substrate having an appropriate guide groove. In addition, both substrate reading and surface reading are possible. Therefore, optical recording media that are fully compatible with existing CDs, DVDs, and next-generation optical discs (so-called DVR-Blue, DVD-Blue), such as high or low reflectance type or high-to-low or low-to-high recording, Can provide.

Alternatively, it is possible to provide an inexpensive optical recording medium having a simple film structure, uniform properties and reproducibility, high light resistance and weather resistance, high reliability, and low manufacturing cost.

Claims (17)

A reversible physical change accompanying laser light irradiation of the compound film alone, having at least one layer as a recording film, having a light absorbing organic compound film substantially consisting of at least one or more light absorbing organic compounds (including those complexed with metal complexes). And recording and erasing of information are carried out by means of a rewritable optical information recording medium. The rewritable optical information recording medium according to claim 1, wherein the physical change is a shape change. The data recording is performed by local physical change by irradiation of recording laser light, and data reproduction is performed by detecting a change in the return light intensity of the reproduction laser light of a smaller power than the recording laser light. A data erasing is performed by irradiating at least one or more continuous light or pulsed light having a laser power greater than the power of light and less than the power of the recording laser light. The rewritable optical information recording medium according to claim 1, wherein the light absorbing organic compound is an organic dye compound that absorbs at least one kind of light having a wavelength selected from a wavelength of 350 nm to 850 nm. The rewritable optical information recording medium according to claim 1, wherein the light absorbing organic compound is an organic dye compound having a molecular weight of less than 3,000. 5. The rewritable optical information recording medium according to claim 4, wherein the organic dye compound is selected from at least one of azaanulene compounds (including those complexed with metals). 7. The rewritable method according to claim 6, wherein the wavelength of the laser light used for recording, reproducing, and erasing is in the range of 350 nm to 450 nm, and the organic dye compound is an azaanulene compound represented by the following formula (1). Fluorescent information recording medium. <Formula 1> [Wherein, R ¹ to R ¹⁶ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercap Represents an earthenware, X ^{1 to} X ⁸ each independently represent a nitrogen atom or a substituted or unsubstituted methine group, and each of the substituents on R ¹ to R ¹⁶ and the methine group may be bonded together via a linking group, or a substituted or unsubstituted group It may have an oxygen atom, a substituted or unsubstituted sulfur atom, a substituted or unsubstituted nitrogen atom between the carbon-carbon atoms in the hydrocarbon group substituted hydroxyl group, hydrocarbon group substituted mercapto group and / or hydrocarbon group substituted amino group in the hydrocarbon group, , n represents O or 1, and when n is 0, M is a divalent metal atom or substituent and / or ligand that may have a ligand Is trivalent, or represents a tetravalent metal atom or metalloid atom, n the case of 1, M represents a trivalent metal atom and one hydrogen atom or a tetravalent metal atom; 8. The rewritable material according to claim 7, wherein the wavelength of the laser light used for recording, reproducing, and erasing is in the range of 350 nm to 450 nm, and the organic dye compound is a tetraazaporphyrin compound represented by the following formula (2). Fluorescent information recording medium. <Formula 2> [Wherein, R ¹⁷ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercap Represents an earth group, and each substituent of R ¹⁷ to R ²⁴ may be bonded together via a linking group with each substituent on the tetraazaporphyrin ring to form an aliphatic ring, a hydrocarbon group substituted hydroxyl group in a substituted or unsubstituted hydrocarbon group, May have an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom between carbon-carbon atoms in a hydrocarbon-substituted mercapto group and / or a hydrocarbon-substituted amino group, M ¹ is a divalent metal atom which may have a ligand or A trivalent or tetravalent metal atom or a semimetal atom having a substituent and / or a ligand] 7. The rewritable method according to claim 6, wherein the wavelength of the laser light used for recording, reproducing, and erasing is in the range of 600 nm to 700 nm, and the organic pigment compound is an azaanulene compound represented by the following formula (3): Fluorescent information recording medium. <Formula 3> [Wherein, R ²⁵ to R ⁴⁰ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercap Represents earthenware, X ^{9 to} X ¹⁶ each independently represent a nitrogen atom or a substituted or unsubstituted methine group having a group or atom represented by R ¹ to R ¹⁶ , and each substituent on R ²⁵ to R ⁴⁰ and a methine group is a linking group Or an aliphatic ring may be bonded to each other to form an aliphatic ring, and an oxygen atom between a carbon-carbon atom in a hydrocarbon group-substituted hydroxyl group, a hydrocarbon group-substituted mercapto group and / or a hydrocarbon group-substituted amino group in a substituted or unsubstituted hydrocarbon group, It may have a substituted or unsubstituted sulfur atom, a substituted or unsubstituted nitrogen atom, n represents O or 1, when n is 0, M ² is A divalent metal atom or substituent which may have a ligand and / or a trivalent or tetravalent metal atom or a semimetal atom having a ligand, when n is 1, M ² represents a trivalent metal atom and one hydrogen atom or Represents a tetravalent metal atom] 7. The rewritable material according to claim 6, wherein the wavelength of the laser light used for recording, reproducing, and erasing is in the range of 600 nm to 700 nm, and the organic dye compound is a tetraazaporphyrin compound represented by the following formula (2). Fluorescent information recording medium. 7. The rewritable light according to claim 6, wherein the wavelength of the laser light used for recording, reproducing, and erasing is in the range of 750 nm to 850 nm, and the organic dye compound is a phthalocyanine compound represented by the following formula (4). Information recording medium. <Formula 4> [Wherein, R ⁴¹ to R ⁷² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted hydroxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted mercap Each of the substituents on R ⁴¹ to R ⁷² and the methine group may be bonded together via a linking group, or a hydrocarbon group-substituted hydroxyl group, a hydrocarbon group-substituted mercapto group, and / or a hydrocarbon group in a substituted or unsubstituted hydrocarbon group. It may have an oxygen atom, a sulfur atom, a substituted or unsubstituted nitrogen atom between carbon-carbon atoms in the group-substituted amino group, n represents 0 or 1, and when n is 0, M ³ may have a ligand divalent metal atom, or a substituent and / or represents a trivalent or a 4-valent metal atoms, semi-metal atom having a ligand, n the case of 1, M ³ is a trivalent metal atom and 1 can It represents an atom or a tetravalent metal atom; The rewritable optical information recording medium according to claim 1, further comprising a transparent protective layer between the light absorbing organic compound recording film and the substrate or adjacent to one side or both sides of the light absorbing organic compound recording film. 13. The rewritable optical information recording medium according to claim 12, wherein the transparent protective layer is formed of at least one selected from inorganic sulfides, inorganic oxides, and inorganic nitrides. Reversible physical accompanying laser light irradiation of the said organic pigment | dye film | membrane body using the rewritable optical information recording medium which has one or more layers as a recording film as the recording film substantially the light absorbing organic compound film which consists only of at least 1 type of light absorbing organic compounds. And recording and erasing information in accordance with the change. 15. The organic dye film as set forth in claim 14, wherein a recording laser light is irradiated on a rewritable optical information recording medium having at least one layer as a light absorbing organic compound film composed substantially of at least one light absorbing organic compound. Data recording is performed by causing a local physical change, and data reproduction is performed by detecting a change in the return light intensity of the reproduction laser light having a power smaller than that of the recording laser light, and a laser power larger than the power of the reproduction laser light and smaller than the power of the recording laser light. And erasing the data by eliminating the physical change by irradiating the continuous light or the pulsed light having at least one or more times. The recording and reproducing method according to claim 14, wherein the physical change is a shape change. A rewritable optical information recording medium having at least one layer of a light absorbing organic compound film composed substantially of at least one light absorbing organic compound as a recording film, and reversible accompanying laser light irradiation of the light absorbing organic compound film alone. And recording / erasing of information by physical change.